JP7178817B2 - Monomers, polymers, compensation films, optical films and display devices - Google Patents

Description

The present invention relates to monomers, polymers, compensation films, optical films and display devices.

Colorless and transparent materials are being researched for various purposes such as optical lenses, functional optical films, disc substrates, etc. However, due to the rapid reduction in size and weight of information equipment and the high density of display elements, materials themselves are required. Functions and performance are also becoming more precise and sophisticated at the same time.

Therefore, active research is currently being conducted on colorless and transparent materials that are excellent in transparency, heat resistance, mechanical strength and flexibility.

US7396898

One embodiment provides novel monomers that can be applied to compensation films.

Other embodiments provide polymers obtained by polymerizing the novel monomers.

Yet another embodiment provides a compensation film comprising the polymer.

Yet another embodiment provides an optical film comprising the compensation film.

Yet another embodiment provides a display device including the compensation film or the optical film.

One embodiment provides a monomer represented by Formula 1 below:

In the above chemical formula 1,
R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted 1 to 30 carbon atoms an alkoxy group of, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), -SiR'R"R"' (where R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms) , or a combination thereof, and
o and p are each independently an integer from 0 to 3;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 to 30 carbon atoms,
R ^a is hydrogen, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, hydroxy group, halogen group, nitro -NR'R" (where R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms is an alkyl group), -CO-NR'R" (wherein R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon an arylalkyl group having a number of 7 to 30), -SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms) , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 30 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; can be,
q and r are each independently an integer from 0 to 3;
m is an integer from 0 to 3,
n is an integer from 0 to 20;

In the chemical formula 1,
o and p are each independently 0 or 1;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 to 20 carbon atoms,
R ^a is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a halogen group; , —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms -CO-NR'R" (where R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or -SiR'R"R"' (where R', R", and R"' are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms); ), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; , q and r are each independently an integer of 0 to 2 and 1≤q+r≤2;
m may be 0-2 and n may be an integer of 0-10.

In the chemical formula 1,
L ¹ is O or NH;
A ¹ is a benzene ring,
R ^a is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a halogen group; , —CO—NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or arylalkyl group), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted benzene ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m may be 0 or 1, and n may be an integer from 0-5.

The monomer represented by Chemical Formula 1 may be a monomer represented by Chemical Formula 3 or Chemical Formula 4 below:

［化学式３］

[Chemical Formula 3]

In the above chemical formulas 3 and 4,
R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted 1 to 30 carbon atoms an alkoxy group of, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), -SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms), or a combination thereof;
o and p are each independently an integer from 0 to 3;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 to 30 carbon atoms,
R ^a is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms ), —CO—NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms -SiR'R"R"' (where R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, a carbon an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 30 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; can be,
q and r are each independently an integer from 0 to 3;
m is 0 to 3,
n is an integer from 0 to 20;
In the chemical formulas 3 and 4,
o and p are each independently 0 or 1;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 to 20 carbon atoms,
R ^a is hydrogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, halogen -NR'R" (where R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms is an alkyl group), -CO-NR'R" (wherein R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon an arylalkyl group having a number of 7 to 30), -SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms) , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; can be,
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m may be 0 or 1, and n may be an integer from 0-10.

In the chemical formulas 3 and 4,
o and p are all 0;
L ¹ is O or NH;
A ¹ is a benzene ring,
R ^a is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a halogen group, —CO—NR′R″ (where R′ and Each R″ is independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or represented by the following chemical formula 2 can be a group:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted benzene ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m may be 0 or 1, and n may be an integer from 0-5.

In another embodiment, there is provided a polymer that is the product of a reactant comprising a monomer according to one embodiment and a diamine.
The diamine may be represented by Formula 5 below:
[Chemical Formula 5]
_{NH2 -} Rc- ^NH2
In the above chemical formula 5,
R ^c includes a substituted or unsubstituted aromatic organic group having 6 to 30 carbon atoms, and the substituted or unsubstituted aromatic organic group having 6 to 30 carbon atoms exists as one substituted or unsubstituted aromatic ring. two or more substituted or unsubstituted aromatic rings are joined together to form a condensed ring; or two or more rings selected from said one aromatic ring and/or said condensed ring are singly a bond, or a fluorenylene group, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, -O-, -S-, -C(=O)- , —CH(OH)—, —S(=O) ₂ —, —Si(CH ₃ ) ₂ —, —(CH ₂ ) _p — (where 1≦p≦10), —(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or combinations thereof. obtain.

The diamine represented by Formula 5 may be represented by one or more of Formulas 6 to 8 below:

In the above chemical formula 6,
R ^d is selected from the group consisting of:

R ⁷ and R ⁸ are the same or different from each other, and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²⁰⁰ , where R ²⁰⁰ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different and each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n1 and n2 are each independently an integer from 0 to 4;
* indicates a connecting point;

In the above chemical formula 7,
R ²⁶ and R ²⁷ are the same or different and each independently -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ or -CO ₂ an electron withdrawing group _selected from _C2H5 ;
R ²⁸ and R ²⁹ are the same or different from each other and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²⁰⁴ , where R ²⁰⁴ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different and each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,
n4 is an integer from 1 to 4, n6 is an integer from 0 to 3, and n4+n6 is an integer from 1 to 4;

In the above chemical formula 8,
R ¹⁴ is O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (where 1 ≤ p ≤ 10), (CF ₂ ) _q , where 1 ≤ q ≤ 10, C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , C(=O)NH, or a substituted or unsubstituted C6-C18 aromatic organic group; whether said C6-C18 aromatic organic group exists as one aromatic ring; two or more aromatic rings are joined together to form a condensed ring; or said one aromatic ring and/or said condensed ring two or more rings selected from a single bond, or a fluorenylene group, O, S, C(=O), CH(OH), S(=O) ₂ , Si( _CH3 ) ₂ , ( _CH2 ) _p (where 1≤p≤10), (CF2) _q (where _{1≤q≤10), C(CH3)2, C(CF3)2 , C ( =} O)NH, or linked by functional groups selected from or combinations thereof,
R ¹⁶ and R ¹⁷ are the same or different from each other and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²¹² , where R ²¹² is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²¹³ R ²¹⁴ R ²¹⁵ , wherein R ²¹³ , R ²¹⁴ and R ²¹⁵ are the same or different from each other and are each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n9 and n10 are each independently an integer of 0-4.

The polymer according to one embodiment may be a reaction product including at least one of the diamine represented by Formula 7 and the diamine represented by Formula 8.

The diamine represented by Formula 7 includes 2,2′-bis(trifluoromethyl)benzidine (TFDB), and the diamine represented by Formula 8 is 4,4 '-diaminodiphenyl sulfone (4,4'-diaminodiphenyl sulfone, DADPS) may be included.

The polymer according to one embodiment may be a reactant product further comprising a dianhydride represented by Formula 9 below:

In the above chemical formula 9,
R ¹⁰ is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -C(=O)NH-, -S(=O) ₂ -, - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p -, -(CF ₂ ) _q -, -C(C _n H _2n+1 ) ₂ -, -C(C _n F _2n+1 ) ₂ -, -(CH ₂ ) _p —C(C _n H _2n+1 ) ₂ —(CH ₂ ) _q —, or —(CH ₂ ) _p —C(C _n F _2n+1 ) ₂ —(CH ₂ ) _q —, where 1≦n≦ 10, 1≤p≤10, and 1≤q≤10) groups;
R ¹² and R ¹³ each independently represent a halogen, a hydroxy group, a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms, - OR ²⁰¹ group (wherein R ²⁰¹ is an aliphatic organic group having 1 to 10 carbon atoms), or —SiR ²¹⁰ R ²¹¹ R ²¹² (wherein R ²¹⁰ , R ²¹¹ and R ²¹² are each independently hydrogen or an aliphatic organic group having 1 to 10 carbon atoms) group,
n7 and n8 are each independently one of the integers from 0 to 3;

The dianhydride represented by the chemical formula 9 may include a dianhydride represented by the following chemical formula 10, a dianhydride represented by the following chemical formula 11, or a combination thereof:

In the above chemical formulas 10 and 11,
R ¹² and R ¹³ are the same or different from each other, each independently halogen, hydroxy group, alkoxy group (-OR ²⁰⁸ , where R ²⁰⁸ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other and are each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n7 and n8 are each independently an integer of 0-3.

The polymer comprises a monomer according to one embodiment and one or more of the dianhydride represented by Formula 10 and the dianhydride represented by Formula 11 in a molar ratio of about 90:10 to about 10:90. may be the product of a reactant comprising in

The polymer according to one embodiment may be a reaction product further comprising a dicarboxylic acid derivative represented by Formula 12 below:

In the above chemical formula 12,
R ³ is a substituted or unsubstituted phenylene group and/or a substituted or unsubstituted biphenylene group, and each X is the same or different halogen atom.

In Formula 12, R ³ is an unsubstituted phenylene group and/or an unsubstituted biphenylene group, and each X may independently be Cl or Br.

Yet another embodiment provides a compensation film comprising a polymer according to one embodiment.

Yet another embodiment provides an optical film comprising a compensation film according to the above embodiments and a polarizer.

Yet another embodiment provides a display including a compensation film according to one embodiment.

Yet another embodiment provides a display device including an optical film according to one embodiment.

The novel monomers according to one embodiment can be reacted with diamines to produce polyester-imide films with high transmittance, low yellowness index, and low haze, and high through-thickness birefringence, and are inexpensive. Since it can be easily produced from a raw material, it can be advantageously used for producing an optical film that requires high optical properties and mechanical properties.

1 is a schematic cross-sectional view of an optical film according to one embodiment; FIG. FIG. 2 is a schematic diagram showing the principle of anti-reflection of external light of an optical film; It is the schematic which showed an example of the polarizing film. 1 is a schematic cross-sectional view of an organic light emitting diode display according to an embodiment; FIG. 1 is a schematic cross-sectional view of a liquid crystal display device according to an embodiment; FIG.

The embodiment will be described in detail below.

Embodiments will be described in detail below so that a person having ordinary knowledge in the technical field can easily implement them. However, embodiments may be embodied in many different forms and are not limited to the embodiments set forth herein.

In the drawings, the thicknesses are exaggerated for clarity of the various layers and regions. The same reference numerals are used for similar parts throughout the specification. When a part such as a layer, film, region, plate, etc. is said to be "on" another part, it means not only that it is "directly above" another part, but also that there is another part in between. include. Conversely, when a part is said to be "directly on" another part, it means that there is no other part in between.

Unless otherwise defined herein, 'substituted' means that at least one hydrogen atom in a compound or functional group is a halogen atom, hydroxy group, alkoxy group, nitro group, cyano group, amino group, azido group, group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, carboxyl group and its salts, sulfonic acid group and its salts, phosphoric acid and its salts, C 1-20 alkyl groups , an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and 1 carbon atom. -20 heteroalkyl group, heteroarylalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, cycloalkenyl group having 3 to 15 carbon atoms, cycloalkynyl group having 6 to 15 carbon atoms, cycloalkynyl group having 6 to 15 carbon atoms It means substituted with substituents selected from 3 to 30 heterocycloalkyl groups and combinations thereof.

In addition, unless otherwise defined herein, 'hetero' means containing 1 to 3 heteroatoms selected from N, O, S, Se and P.

Optically transparent heat-resistant polymers are materials that are usefully applied to various optoelectronic devices such as imaging devices, liquid crystal alignment films, color filters, optical compensation films, optical fibers, light guide plates, and optical lenses. . A recent hot topic in this regard is the significantly lighter weight replacement of fragile inorganic glass substrates (e.g., about 300 nm to 700 mm thick) with plastic substrates (<50 mm thick) in imaging devices. to realize a flexible display panel.

However, in the case of plastic substrates, optical transmittance, heat resistance, dimensional stability against thermal cycles during the device assembly process (thermal dimensional stability), film flexibility, and film formation process compatibility (solution process) are high. Since it is difficult to achieve both standards at the same time, the reality is that it is difficult to ensure reliability. Plastic substrates are generally superior to inorganic glass substrates in terms of flexibility and thin film formability, but are inferior in terms of heat resistance and thermal dimensional stability.

Poly(ethersulfone) (PES) is known to have the highest glass transition temperature (Tg, 225° C.) among commercially available super engineering plastics. However, PES is not suitable in terms of short-term heat resistance and thermal dimensional stability. A plastic substrate with poor thermal dimensional stability will undergo considerable thermal expansion/contraction during repeated heating/cooling cycles during the process of forming Indium Tin Oxide (ITO) electrodes and thin film transistors, which is due to the ITO It can cause serious problems such as layer collapse.

Polyimide (PI) is one of the most reliable high temperature polymer materials. Some aromatic PI systems simultaneously have a higher Tg than the device operating temperature and a low linear coefficient of thermal expansion (CTE) along the film plane (XY) direction within the vitreous region. It may also have excellent thermal dimensional stability. However, ordinary aromatic PIs exhibit strong coloration caused by charge transfer (CT) interactions, which sometimes disturb optical devices. The coloring/bleaching mechanism of aromatic PI films has been the subject of extensive academic and industrial research. One of the effective approaches for decolorization is to prevent CT interactions by choosing non-aromatic (alicyclic) monomers from diamines or tetracarboxylic dianhydrides or both. . However, the use of cycloaliphatic monomers poses some serious problems. That is, despite the high glass transition temperature Tg (>300° C.) of the partially or wholly alicyclic PI film, the high coefficient of linear thermal expansion CTE (>60 ppm K ⁻¹ ) within the vitreous region results in Sometimes has poor thermal dimensional stability. Such a high coefficient of linear thermal expansion actually arises from the randomly arranged chain orientation in three dimensions. The majority of alicyclic monomers consist of non-linear/non-planar conformations. As a result, the linearity of the PI backbone is completely destroyed. Such a twisted backbone structure is not highly aligned in chain orientation along the XY direction (hereinafter "planar orientation") during the thermal imidization process. Among alicyclic monomers, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA, 1,2,3,4-cyclobutanetetracarboxylic dianhydride) and trans-1,4-cyclohexanediamine (t-CHDA, trans-1,4-cyclohexanediamine) is a rare case of a tonic and linear structure. However, the final PI using such monomers is not solution processable. On the other hand, 4,4′-(hexafluoroisopropylidene) (6FDA, 4,4′-(hexafluoroisopropylidene) diphthalic anhydride) and 2,2′-bis(trifluoromethyl)benzidine (TFMB, bis(trifluoromethyl)benzidine) The derived wholly aromatic PI system has high transparency and excellent solubility despite not having a low linear thermal expansion coefficient due to the non-linear/non-coplanar conformation of the 6-FDA-based diimide units. is a restrictive case for

Therefore, it is very difficult to develop a highly reliable plastic substrate that satisfies various target properties at the same time.

The present inventors have synthesized novel monomers capable of producing polyimides that simultaneously satisfy thermal stability and optical transparency, and the polymers produced from these monomers exhibit specific optical properties, such as high transparency and high thickness. The inventors have completed the present invention by confirming that the material has out-of-plane birefringence and high thermal stability due to its high glass transition temperature. The monomer may be represented by Chemical Formula 1 below:

In the above chemical formula 1,
R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted 1 to 30 carbon atoms an alkoxy group of, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), -SiR'R"R"' (where R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms) , or a combination thereof, and
o and p are each independently an integer from 0 to 3;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 to 30 carbon atoms,
R ^a is hydrogen, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, hydroxy group, halogen group, nitro -NR'R" (where R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms is an alkyl group), -CO-NR'R" (wherein R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon an arylalkyl group having a number of 7 to 30), -SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms) , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 30 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; can be,
q and r are each independently an integer from 0 to 3;
m is an integer from 0 to 3,
n is an integer from 0 to 20;

According to one embodiment, the compound represented by Formula 1 has a rigid planar structure in which the dianhydride groups on both sides of the core are connected by carbonyl groups (C=O). while having a higher molecular volume and an asymmetric structure to improve solubility and reduce intermolecular stacking and charge transfer by including bulky substituents in the side chains of the core. Thereby, the optical properties can also be improved.

A rigid planar structure is advantageous in having a lower linear thermal expansion coefficient, a higher glass transition temperature, a higher through-thickness birefringence, higher mechanical properties, etc., which allows molecules to form a laminated structure. by forming an intermolecular charge-transfer complex, the polymer produced therefrom becomes yellowish and has unfavorable optical properties. In the case of the compound represented by Chemical Formula 1 according to the above embodiment, although it has a rigid planar structure as a whole, the inclusion of bulky substituents in the side chains of the core facilitates the formation of intermolecular complexes and charge-transfer complexes. While reducing the resulting optical property degradation, the overall planar structure maintains high thermal stability, low linear thermal expansion coefficient, high through-thickness birefringence, and excellent mechanical properties. can. Therefore, according to one embodiment, a novel dianhydride containing an ester structure in which the core has a bulky side chain and the dianhydride groups on both sides are bonded to the core by a carbonyl group is produced by reflecting it as an aromatic diamine. Polyester-imide polymers can combine high thermal stability and excellent optical properties. Furthermore, as will be seen through the examples below, the compounds according to the above embodiments can be produced at a low cost from readily available and inexpensive starting materials, thereby exhibiting excellent existing optical properties and mechanical properties. There is also an effect that the manufacturing cost can be reduced compared to aromatic diamines or aromatic dianhydrides.

In one embodiment, o and p in Formula 1 may each independently be 0 or 1,
L ¹ can be O or NR ^b (wherein R ^b is hydrogen or a C 1-20 alkyl group), for example O or NH;
A ¹ is an aromatic organic group having 6 to 30 carbon atoms, such as an aromatic organic group having 6 to 20 carbon atoms, such as an aromatic organic group having 6 to 12 carbon atoms, such as an aromatic organic group having 6 to 10 carbon atoms. may be an organic group, such as a benzene ring,
R ^a is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, a halogen group; , —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms -CO-NR'R" (where R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or -SiR'R"R"' (where R', R", and R"' are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms); ), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms), such as COO, C ≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms), for example, COO, C≡C, or CONH;
A ² and A ³ are each independently a substituted or unsubstituted C 6-20 aromatic ring group, such as a substituted or unsubstituted C 6-16 aromatic ring, such as a substituted or unsubstituted an aromatic ring having 6 to 12 carbon atoms, such as a benzene ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, such as a substituted or unsubstituted can be a phenylalkyl group, such as a phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, or phenylpentyl group,
q and r can each independently be an integer from 0 to 2 and 1 ≤ q + r ≤ 2;
m can be 0-2, such as 0 or 1;
n can be an integer from 0-10, such as an integer from 0-5, such as an integer from 0-3, such as an integer from 0-2.

The monomer represented by Formula 1 may be a monomer represented by Formula 3 or Formula 4 below:

In the above chemical formulas 3 and 4,
R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted 1 to 30 carbon atoms an alkoxy group of, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), —SiR′R″R″, where R′, R″, and R′″ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms, or a combination thereof;
o and p may each independently be an integer from 0 to 3, such as each independently 0 degrees is 1, or for example, o and p may all be 0;
L ¹ can be O or NR ^b (wherein R ^b is hydrogen or a C 1-20 alkyl group), for example O or NH;
A ¹ is an aromatic organic group having 6 to 20 carbon atoms, such as an aromatic organic group having 6 to 16 carbon atoms, such as an aromatic organic group having 6 to 12 carbon atoms, such as an aromatic organic group having 6 to 10 carbon atoms. may be a group organic group, such as a benzene ring,
R ^a is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms ), —CO—NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms -SiR'R"R"' (where R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, a carbon an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms), such as COO, C ≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms), for example, COO, C≡C, or CONH;
A ² and A ³ are each independently a substituted or unsubstituted C 6-30 aromatic ring, such as a substituted or unsubstituted C 6-16 aromatic ring, such as a substituted or unsubstituted an aromatic ring having 6 to 12 carbon atoms, such as a substituted or unsubstituted aromatic ring having 6 to 10 carbon atoms, such as a benzene ring, or a substituted or unsubstituted fluorene ring, such as an unsubstituted fluorene ring or a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, such as a substituted or unsubstituted phenylmethyl group, a substituted or unsubstituted phenylethyl group, a substituted or unsubstituted phenylpropyl group, a substituted or an unsubstituted phenylbutyl group, or a substituted or unsubstituted phenylpentyl group,
q and r may each independently be an integer from 0 to 3, such as each independently an integer from 0 to 2, where 1 ≤ q + r ≤ 2;
m can be 0-3, such as 0-2, such as 0 or 1;
n can be an integer from 0-10, such as an integer from 0-5, such as an integer from 0-3, such as an integer from 0-2.

In Formulas 3 and 4, o and p may each independently be 0 or 1, for example, both o and p may be 0, and L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms),
A ¹ can be an aromatic organic group having 6 to 20 carbon atoms, such as a benzene ring,
R ^a is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a halogen group, —CO—NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or represented by the following chemical formula 2 can be a group:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a benzene ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m can be 0 or 1 and n can be an integer from 0-5.

o and p in Chemical Formulas 3 and 4 are all 0, L ¹ is O or NH, A ¹ is a benzene ring, R ^a is hydrogen, a fluoro group, —CO—NR′R” (here and R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or the following chemical formula can be a group represented by 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONH;
A ² and A ³ are each independently a benzene ring, a fluorene ring, or an arylalkyl group having 7 to 20 carbon atoms;
q and r are each independently an integer of 0 or 1 and 0≤q+r≤1;
m may be an integer of 1;

Specific examples of the monomers according to one embodiment include, but are not limited to, compounds represented by compounds M-1 to M-20 below:

In one embodiment, the compound in which L1 is O and n is ¹ in the monomer represented by Formula 3 can be prepared according to Reaction Formula 1 below:

In one embodiment, the compound in which L1 is O and n is ¹ in the monomer represented by Formula 4 can be prepared according to Reaction Formula 2 below:

In “R—CH ₂ —Hal” in Reaction Schemes 1 and 2, “R—” corresponds to the portion represented by “(R ^a )mA ¹ —” in Chemical Formula 3, and “Hal "" means a halogen atom such as F, Cl, Br, I, etc. "DMAC" means the solvent "dimethylacetamide" and "MeCN" means "methyl cyanide".

In ^one embodiment, when L1 is O or NH and n is 0 or 1 in the monomer represented by Formula 3, it can be prepared according to Reaction Formula 3 below:

In ^one embodiment, when L1 is O or NH and n is 0 or 1 in the monomer represented by Formula 4, it can be prepared according to Reaction Formula 4 below:

In Reaction Schemes 3 and 4, Ac ₂ O is acetic anhydride, OAc is acetate group, PhMe is toluene, DCM is dichloromethane, R ^a , A ¹ , L ¹ , m, n, R ¹ and o are all defined in Formula 3 and Formula 4 above.

That is, the monomer according to one embodiment can be easily prepared according to the above reaction scheme by a person of ordinary skill in the art using starting materials that are commercially available at low cost.

Said monomer is a dianhydride compound with both anhydride ends and can therefore be reacted with an equal molar amount of a diamine compound to form a polyimide.

Accordingly, in another embodiment there is provided a polymer that is the product of a reactant comprising a monomer and a diamine according to one embodiment.

The diamine may be represented by Formula 5 below:
[Chemical Formula 5]
_{NH2 -} Rc- ^NH2
In the above chemical formula 5,
R ^c includes a substituted or unsubstituted aromatic organic group having 6 to 30 carbon atoms, and the substituted or unsubstituted aromatic organic group having 6 to 30 carbon atoms exists as one substituted or unsubstituted aromatic ring. two or more substituted or unsubstituted aromatic rings are joined together to form a condensed ring; or two or more rings selected from said one aromatic ring and/or said condensed ring are singly a bond, or a fluorenylene group, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, -O-, -S-, -C(=O) -, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (where 1≤p≤10), -(CF ₂ ) linked by functional groups that are _q- , where 1≤q≤10, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or combinations thereof can be

The polymer prepared by reacting the monomer according to the embodiment with the diamine represented by Formula 5 may include a first imide structural unit represented by Formula 13 below:

In Chemical Formula 13, R ^a , A ¹ , L ¹ , m, n, R ¹ , R ² , o, and p are all defined in Chemical Formula 1 above, and R ^c is defined in Chemical Formula 5 above. is.

When the monomer according to one embodiment is the monomer represented by Formula 3, the first imide structural unit may be represented by Formula 14 below:

When the monomer according to one embodiment is the monomer represented by Formula 4, the first imide structural unit may be represented by Formula 15 below:

In Chemical Formula 14 and Chemical Formula 15, R ^a , A ¹ , L ¹ , m, n, R ¹ , R ² , o, and p are all defined in Chemical Formula 1 above, and R ^c is defined in Chemical Formula 5 above. As defined.

The diamine represented by Formula 5 may be represented by one or more of Formulas 6 to 8 below:

In the above chemical formula 6,
R ^d is selected from the group consisting of:

R ⁷ and R ⁸ are the same or different from each other, and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²⁰⁰ , where R ²⁰⁰ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different and each independently hydrogen or an aliphatic organic group), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n1 and n2 are each independently an integer of 0 to 4;
* indicates a connecting point;

In the above chemical formula 7,
R ²⁶ and R ²⁷ are the same or different and each independently -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ or -CO ₂ an electron withdrawing group _selected from _C2H5 ;
R ²⁸ and R ²⁹ are the same or different from each other and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²⁰⁴ , where R ²⁰⁴ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different and each independently hydrogen or an aliphatic organic group), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,
n4 is an integer from 1 to 4, n6 is an integer from 0 to 3, and n4+n6 is an integer from 1 to 4;

In the above chemical formula 8,
R ¹⁴ is O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (where 1 ≤ p ≤ 10), (CF ₂ ) _q , where 1≦q≦10, C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , C(═O)NH, or substituted or unsubstituted C 6-180 aromatic organic wherein said C6-C18 aromatic organic group is present as one aromatic ring; two or more aromatic rings are joined together to form a fused ring; or said one aromatic ring and/or or two or more rings selected from the condensed rings are a single bond, a fluorenylene group, O, S, C(=O), CH(OH), S(=O) ₂ , Si( _CH3 ) ₂ , (CH ₂ ) _p (where 1≦p≦10), (CF ₂ ) _q (where 1≦q≦10), C(CH ₃ ) ₂ , C(CF ₃ ) ₂ or C(= O) is linked by a functional group of NH,
R ¹⁶ and R ¹⁷ are the same or different from each other and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²¹² , where R ²¹² is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²¹³ R ²¹⁴ R ²¹⁵ , wherein R ²¹³ , R ²¹⁴ and R ²¹⁵ are the same or different from each other and are each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n9 and n10 are each independently an integer of 0-4.

The polymer according to one embodiment includes at least one of the diamine represented by Formula 7 and the diamine represented by Formula 8, wherein the diamine represented by Formula 7 is 2,2′-bis( 2,2′-bis(trifluoromethyl)benzidine (TFDB), and the diamine represented by Formula 8 is 4,4′-diaminodiphenyl sulfone (DADPS). can be the product of a reactant comprising

When the polymer according to one embodiment is prepared by reacting the monomer represented by Formula 1 with TFDB as a diamine, the first imide structural unit may include a structural unit represented by Formula 16 below:

When the polymer according to one embodiment is prepared by reacting the monomer represented by Formula 1 with DADPS as a diamine, the first imide structural unit may include a structural unit represented by Formula 17 below:

In Chemical Formula 16 and Chemical Formula 17, R ^a , A ¹ , L ¹ , m, n, R ¹ , R ² , o, and p are all defined in Chemical Formula 1 above.

The polymer according to one embodiment may be a reaction product that further includes a compound represented by the following Formula 9 as a dianhydride compound in addition to the monomer represented by Formula 1 according to one embodiment:

In the above chemical formula 9,
R ¹⁰ is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -C(=O)NH-, -S(=O) ₂ -, - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p , -(CF ₂ ) _q , -C(C _n H _2n+1 ) ₂ -, -C(C _n F _2n+1 ) ₂ -, -(CH ₂ ) _p -C( _CnH2n+1 ) _2- ( _CH2 ) _q- , or -( _CH2 ) _p -C _{( CnF2n +1} ) _2- ( _CH2 ) _q- , where 1≤n≤10, 1 ≤ p ≤ 10 and 1 ≤ q ≤ 10 groups),
R ¹² and R ¹³ each independently represent a halogen, a hydroxy group, a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms, - OR ²⁰¹ group (wherein R ²⁰¹ is an aliphatic organic group having 1 to 10 carbon atoms), or —SiR ²¹⁰ R ²¹¹ R ²¹² (wherein R ²¹⁰ , R ²¹¹ and R ²¹² are each independently hydrogen or an aliphatic organic group having 1 to 10 carbon atoms) group,
n7 and n8 are each independently one of the integers from 0 to 3;

The dianhydride represented by Chemical Formula 9 may include a dianhydride represented by Chemical Formula 10, a dianhydride represented by Chemical Formula 11, or a combination thereof:

In the above chemical formulas 10 and 11,
R ¹² and R ¹³ are the same or different from each other, each independently halogen, hydroxy group, alkoxy group (-OR ²⁰⁸ , wherein R ²⁰⁸ is an aliphatic organic group having 1 to 10 carbon atoms); , a silyl group (—SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other and are each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms, a), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n7 and n8 are each independently an integer of 0-3.

When the polymer according to one embodiment is a product of a reactant further including the dianhydride represented by Formula 9, the polymer may further include a second imide structural unit represented by Formula 18 below. :

In Formula 18, R ¹⁰ , R ¹² , R ¹³ , n7, and n8 are as defined in Formula 9 above, and R ^c is as defined in Formula 5 above.

The second imide structural unit represented by Chemical Formula 18 may include a structural unit represented by Chemical Formula 19 below, a structural unit represented by Chemical Formula 20 below, or a combination thereof:

In Formulas 19 and 20, R ¹² , R ¹³ , n7, and n8 are all defined in Formula 9 above, and R ^c is defined in Formula 5 above.

The polymer according to one embodiment may be a product of a reactant further including a dicarboxylic acid derivative represented by Formula 12 below:

In the above chemical formula 12,
R ³ is a substituted or unsubstituted phenylene group and/or a substituted or unsubstituted biphenylene group, and each X is the same or different halogen atom.

In Formula 12, R ³ is an unsubstituted phenylene group and/or an unsubstituted biphenylene group, and each X may independently be Cl or Br.

When the polymer according to one embodiment is a product of a reaction product further including the dicarboxylic acid derivative represented by Formula 12, the dicarboxylic acid derivative reacts with the diamine represented by Chemical Formula 5, and is represented by Chemical Formula 21 below. can form an amide structural unit with:

In Formula 21, Rc is as defined in Formula ⁵ above, and ^R3 is as defined in Formula 12 above.

In one embodiment, the polymer according to the above embodiment includes TFDB as a diamine, and the dicarboxylic acid derivative represented by Formula 3 is terephthaloyl chloride (TPCl), wherein R ³ is a phenylene group and X is Cl. ), the structural unit represented by Formula 21 can include a structural unit represented by Formula 22 below:

In one embodiment, the polymer according to the above embodiments includes DADPS as a diamine, and the dicarboxylic acid derivative represented by Formula 3 is terephthaloyl chloride (TPCl), wherein R ³ is a phenylene group and X is Cl. ), the structural unit represented by Formula 21 can include a structural unit represented by Formula 23 below:

The polymer may comprise a monomer according to one embodiment, such as the monomer represented by Formula 3, the monomer represented by Formula 4, or a combination thereof, and the dianhydride represented by Formula 9, such as The dianhydride represented by Formula 10, the dianhydride represented by Formula 11, or a combination thereof in a molar ratio of about 90:10 to about 10:90, such as about 85:15 to about 15:85. ratio, such as a molar ratio of about 20:80 to about 80:20, such as a molar ratio of about 25:75 to about 75:25, such as a molar ratio of about 30:70 to about 70:30, such as a molar ratio of about a molar ratio of 35:65 to about 65:35, such as a molar ratio of about 40:60 to about 60:40, such as a molar ratio of about 45:55 to about 55:45, such as a molar ratio of about 50:50 It can be a product of reactants containing ratios.

By appropriately controlling the ratio of the monomer according to one embodiment and the dianhydride represented by Formula 9 within the above range, a polyimide-based polymer having desired optical properties and high heat resistance can be produced.

The polymer can be prepared, for example, in film form and used as a polymer film. The polymer film may for example be transparent and can be used in any application where transparency is required. Polymer films can be used in a variety of applications, such as substrates, protective films, compensation films, optical films, dielectric layers, insulating layers, and adhesive layers.

A compensation film according to one embodiment is described below.

A compensation film according to one embodiment comprises the aforementioned polymer.

That is, the compensation film according to one embodiment is prepared by reacting the monomer according to one embodiment, that is, the monomer represented by Chemical Formula 1 with diamine, and the compound represented by one or more of Chemical Formulas 13 to 17 is prepared. A polyimide-based polymer containing one imide structural unit can be included.

Alternatively, the compensation film may include a polyimide-based polymer that is a product of a reaction product further including the dianhydride represented by Chemical Formula 9, which is an additional dianhydride other than the monomer represented by Chemical Formula 1. In addition to the first imide structural unit, the polymer may further include a second imide structural unit represented by one or more of Formulas 18-20.

Further, the compensation film may include a poly(amide-imide) polymer, which is a reaction product further including the dicarboxylic acid derivative represented by Formula 12, and the polymer has the first imide structure In addition to the units, amide structural units represented by one or more of Formulas 21 to 23 may be further included.

In one embodiment, the compensation film comprises a first imide structural unit represented by one or more of Chemical Formulas 13 to 17 and a second imide structural unit represented by one or more of Chemical Formulas 18 to 20. Poly(amide-imide) copolymers including structural units and amide structural units represented by one or more of Formulas 21 to 23 may be included.

In addition to said structural units, the polymer according to one embodiment optionally together with said first imide structural unit is a reaction product of additional non-limiting dianhydrides, diamines and/or dicarboxylic acid derivatives monomers It can further contain a structural unit that is Additional dianhydride, diamine, and/or dicarboxylic acid derivative monomers enhance the functionality of molded articles made from polymers or copolymers made therefrom, such as optical films, such as compensation films. Any type can be used together as long as it can be used, and there is no particular limitation.

A film made from a polymer according to one embodiment exhibits high thermal stability, e.g., a high glass transition temperature, e.g., a glass transition temperature of about 150°C or higher, e.g. A glass transition temperature of 170° C. or higher, such as a glass transition temperature of about 180° C. or higher, such as a glass transition temperature of about 190° C. or higher, such as a glass transition temperature of about 200° C. or higher, such as a glass transition temperature of about 210° C. or higher It may have a temperature, such as a glass transition temperature of about 220° C. or higher, such as a glass transition temperature of about 230° C. or higher, such as a glass transition temperature of about 240° C. or higher, such as a glass transition temperature of about 250° C. or higher.

Films made from the polymer according to one embodiment also have excellent optical properties, e.g., high light transmission at 450 nm, e.g. , a transmission of 87% or more, such as a transmission of 88% or more, such as a transmission of 89% or more, such as a transmission of 90% or more.

Also, the film made from the polymer according to one embodiment has a thickness of 100 μm or less, such as 90 μm or less, such as 80 μm or less, such as 70 μm or less, such as 60 μm or less, such as 50 μm or less, such as 40 μm or less, such as A high through-thickness birefringence, such as a birefringence of about 0.03 or more, such as a birefringence of about 0.04 or more, such as a birefringence of about 0.04 or more, at a thin film thickness of 30 μm or less, such as 20 μm or less. 05 or greater, such as about 0.06 or greater, such as about 0.07 or greater, such as about 0.08 or greater, such as about 0.09 or greater can have a birefringence of

Thus, films made from polymers according to one embodiment exhibit high thermal stability, e.g., high glass transition temperatures, and excellent optical properties, e.g., high optical transmission at 450 nm and high through-thickness birefringence. It is useful for use as an optical film such as a compensation film by exhibiting a high birefringence in the thickness direction at a thin film thickness of 100 μm or less.

When the film is used as a compensating film, the compensating film can have a predetermined retardation by changing the light absorption characteristics depending on the refractive index and wavelength.

The retardation (R) of the compensation film can be represented by the in-plane retardation (R _o ) and the thickness direction retardation (R _th ). The in-plane retardation (R _o ) of the compensation film is the retardation occurring in the in-plane direction of the compensation film, and can be expressed as R _o =(n _x -n _y )d. The thickness direction retardation (R _th ) of the compensation film is the retardation occurring in the thickness direction of the compensation film, and is expressed as R _th ={[(n _x +n _y )/2]−n _z }d. obtain. Here, nx is the refractive index in the direction of the largest in-plane refractive index of the compensation film (hereinafter referred to as 'slow _axis '), and ny is the largest in-plane refractive _index of the compensation film. is the refractive index in the small direction (hereinafter referred to as the 'fast axis'), _nz is the refractive index in the direction perpendicular to the slow and fast axes of the compensation film, and d is the compensation film's thickness.

The compensation film can be adjusted to have a predetermined range of in-plane retardation and through-thickness retardation by changing n _x , n _y , n _z and/or thickness (d).

The retardation of the compensation film may be the same or different depending on the wavelength.

As an example, the compensation film may have a positive chromatic dispersion phase retardation in which the retardation for short wavelength light is greater than the retardation for long wavelength light, and when 550 nm wavelength is the reference wavelength, e.g. The retardation (R) of the compensation film for can satisfy the following relational expression 1 or 2.

[Relationship 1]
R (450 nm)≧R (550 nm)>R (650 nm)
[Relational expression 2]
R (450 nm)>R (550 nm)≧R (650 nm)

As an example, the compensation film may have a flat dispersion phase retardation with substantially the same retardation for long wavelength light and for short wavelength light, e.g. The retardation (R) can satisfy the following relational expression 3.

[Relational expression 3]
R (450 nm) = R (550 nm) = R (650 nm)

As an example, the compensation film can have an inverse wavelength dispersion phase retardation in which the retardation for long wavelength light is greater than the retardation for short wavelength light, e.g., the retardation (R ) can satisfy the following relational expression 4 or 5.

[Relational expression 4]
R (450 nm) ≤ R (550 nm) < R (650 nm)
[Relational expression 5]
R (450 nm) < R (550 nm) ≤ R (650 nm)
In the above relational expressions 1 to 5,
R(450nm) is the in-plane or through-thickness retardation of the compensation film for a wavelength of 450nm;
R(550nm) is the in-plane or through-thickness retardation of the compensation film for a wavelength of 550nm;
R(650nm) is the in-plane or through-thickness retardation of the compensation film for the 650nm wavelength.

The compensation film can be adjusted to have a desired retardation according to wavelength.

The compensation film may have a high birefringence and thus a relatively thin thickness. The compensation film can have a thickness of, for example, about 3 μm to 200 μm, within said range, for example, of about 5 μm to 150 μm, within said range, for example, of about 5 μm to 100 μm. can.

Since the compensation film contains a substantially transparent polymer, it can be used as a substrate, thereby eliminating a separate substrate under the compensation film. Therefore, the thickness of the compensation film can be further reduced. Accordingly, it can be effectively applied to a flexible display device such as a foldable display device or a bendable display device to improve optical characteristics and display characteristics.

The compensation film is manufactured, for example, by preparing a monomer according to one embodiment, polymerizing the monomer to prepare a polymer, preparing the polymer as a film, and stretching the film. be able to.

The compensation film can be stretched, for example, at a temperature of 50° C. to 500° C. and a stretch ratio of about 110% to about 1,000%. Here, the stretch ratio refers to the ratio of the length of the compensation film before stretching to the length of the compensation film after stretching, and means the degree of stretching of the compensation film after uniaxial stretching. For example, the compensation film can be uniaxially oriented.

The aforementioned compensation films can be used alone or in conjunction with other compensation films.

The compensation film can be used together with a polarizer to serve as an optical film that prevents reflection of external light from a display device. The optical film can be, for example, an antireflection film, but is not limited to this.

FIG. 1 is a schematic cross-sectional view of an optical film according to one embodiment, FIG. 2 is a schematic view showing the principle of preventing external light reflection of the optical film, and FIG. 3 is a schematic view showing an example of a polarizing film. .

Referring to FIG. 1, an optical film 100 according to one embodiment includes a polarizer 110 and a compensation film 120. As shown in FIG. The compensation film 120 can circularly polarize the light passing through the polarizer 110 to generate a phase difference, and can affect the reflection and/or absorption of light.

For example, the optical film 100 is provided on one side or both sides of the display device, particularly on the screen side of the display device to reflect external light (hereinafter referred to as 'external light reflection'). can be prevented. Therefore, it is possible to prevent deterioration of visibility due to reflection of external light.

FIG. 2 is a schematic diagram showing the principle of antireflection of external light of an optical film.

Referring to FIG. 2, incident unpolarized light passes through a polarizer 110, and only one polarization orthogonal component out of two polarization orthogonal components, i.e., the first polarization orthogonal component, is transmitted; The polarized light is converted to circular polarization while passing through the compensation film 120 . The circularly polarized light is reflected by the display panel 50 including a substrate, electrodes, etc., and the direction of the circularly polarized light is changed. Only one other polarization orthogonal component, the second polarization orthogonal component, can be transmitted. Since the second polarization orthogonal component does not pass through the polarizer 110 and is not emitted to the outside, it may have an external light reflection prevention effect.

Polarizer 110 can be, for example, a polarizing plate or a polarizing film.

Referring to FIG. 3, the polarizer 110 can be, for example, a monolithic polarizing film made from a melt blend of a polymer resin 71 and a dichroic dye 72 .

Polymer resin 71 can be, for example, a hydrophobic polymer resin, such as polyolefins such as polyethylene (PE), polypropylene (PP) and copolymers thereof; polyamides such as nylon and aromatic polyamides; polyethylene terephthalate; (PET), polyethylene terephthalate glycol (PETG) and polyethylene naphthalate (PEN); polyacrylics such as polymethyl (meth)acrylate; polystyrenes such as polystyrene (PS) and acrylonitrile-styrene copolymers; vinyl chloride resin; polyimide; sulfone resin; polyether sulfone; polyether-ether ketone; polyphenylene sulfide; vinyl alcohol resin; or a combination thereof.

Among them, the polymer resin 71 can be, for example, polyolefin resin, polyamide resin, polyester resin, polyacrylic resin, polystyrene resin, copolymers thereof, or combinations thereof, such as polyethylene (PE), polypropylene ( PP), polyethylene terephthalate (PET), polyethylene terephthalate glycol (PETG), polyethylene naphthalate (PEN), nylon, copolymers thereof or combinations thereof.

In this, the polymeric resin 71 may (can?) be a polyolefin. The polyolefin can be, for example, a mixture of at least two selected from polyethylene (PE), polypropylene (PP), copolymers of polyethylene and polypropylene (PE-PP), such as polypropylene (PP) and polyethylene-polypropylene copolymers. It can be a mixture of polymers (PE-PP).

The polymer resin 71 may have a transmittance of about 85% or more in the wavelength range of about 400-780 nm. The polymer resin 71 is uniaxially stretched. The uniaxial direction may be the same as the longitudinal direction of the dichroic dye 72, which will be described later.

The dichroic dye 72 is dispersed in the polymer resin 71 and arranged in one direction along the stretched direction of the polymer resin 71 . The dichroic dye 72 can transmit only one polarization orthogonal component of the two polarization orthogonal components for a given wavelength region.

Dichroic dye 72 may be included in an amount of about 0.01 to 5 parts by weight with respect to 100 parts by weight of polymer resin 71 . By being included in the above range, it is possible to exhibit sufficient polarizing properties without lowering transmittance when formed as a polarizing film. Within this range, it may be included at about 0.05 to 1 part by weight per 100 parts by weight of polymeric resin 71 .

Polarizer 110 has a relatively thin thickness of about 100 μm or less, and may have a thickness of about 30 μm to about 95 μm, for example. By having a thickness within the above range, the thickness can be significantly reduced compared to a polarizing plate that requires a protective layer such as triacetyl cellulose (TAC), thereby realizing a thin display device. be able to.

Compensation film 120 is as previously described.

The optical film 100 may further include a correction layer (not shown) located on one side of the compensation film 120 . The correction layer can be, for example, but not limited to, a color shift resistant layer.

The optical film 100 may further include a light blocking layer (not shown) extending along the perimeter. The light-shielding layer can be formed in the form of a strip along the perimeter of the optical film 100 and can be placed, for example, between the polarizer 110 and the compensation film 120 . The light shielding layer may comprise an opaque material, such as a black material. For example, the light shielding layer can be formed from black ink.

The optical film 100 may be applied to various display devices.

A display device according to one embodiment includes a display panel and an optical film positioned on one side of the display panel. The display panel may be a liquid crystal display panel or an organic light emitting display panel, but is not limited thereto.

An organic light-emitting display device will be described below as an example of a display device.

FIG. 4 is a schematic cross-sectional view of an organic light emitting diode display according to one embodiment.

Referring to FIG. 4 , an organic light emitting display device according to an embodiment includes an organic light emitting display panel 400 and an optical film 100 positioned on one side of the organic light emitting display panel 400 .

The organic light emitting display panel 400 may include a base substrate 410 , a lower electrode 420 , an organic light emitting layer 430 , an upper electrode 440 and an encapsulation substrate 450 .

Base substrate 410 may be manufactured from glass or plastic.

One of the lower electrode 420 and the upper electrode 440 may be an anode and the other one may be a cathode. The anode is an electrode into which holes are injected, and is formed of a transparent conductive material having a high work function and emitting light to the outside, such as ITO or IZO. The cathode is an electrode into which electrons are injected, and is made of a conductive material that has a low work function and does not affect organic materials, such as aluminum (Al), calcium (Ca), and barium (Ba). can be

The organic light emitting layer 430 includes an organic material that emits light when voltage is applied to the lower electrode 420 and the upper electrode 440 .

Additional layers (not shown) may be further included between the lower electrode 420 and the organic light emitting layer 430 and between the upper electrode 440 and the organic light emitting layer 430 . The auxiliary layers include a hole transporting layer, a hole injecting layer, an electron injecting layer and an electron transporting layer for balancing electrons and holes. can include

The encapsulation substrate 450 is made of glass, metal, or polymer, and can seal the lower electrode 420, the organic light emitting layer 430, and the upper electrode 440 to prevent moisture and/or oxygen from entering from the outside. .

The optical film 100 can be placed on the side from which the light exits. For example, in the case of a bottom emission structure in which light is emitted to the side of the base substrate 410, it is arranged outside the base substrate 410 and in the case of a top emission structure in which light is emitted to the side of the encapsulation substrate 450, encapsulation is required. It can be located outside the substrate 450 .

The optical film 100 includes the aforementioned integrated polarizer 110 and integrated compensation film 120 . The polarizer 110 and the compensation film 120 are as described above, respectively, and prevent the light passing through the polarizer 110 from being reflected by metal such as the electrodes of the organic light emitting display panel 400 and exiting the display device, It is possible to prevent deterioration of visibility due to light flowing in from the outside. Therefore, the display characteristics of the organic light emitting diode display can be improved.

A liquid crystal display device will be described below as an example of the display device.

FIG. 5 is a cross-sectional view schematically showing a liquid crystal display device according to one embodiment.

Referring to FIG. 5 , the liquid crystal display device according to one embodiment includes a liquid crystal display panel 500 and optical films 100 positioned on one or both sides of the liquid crystal display panel 500 .

The liquid crystal display panel 500 may be a twist nematic (TN) mode, a patterned vertical alignment (PVA) mode, an in plane switching (IPS) mode, an optically compensating bend (OCB) mode, or the like. .

The liquid crystal display panel 500 includes a first display panel 510 , a second display panel 520 , and a liquid crystal layer 530 interposed between the first display panel 510 and the second display panel 520 .

The first display panel 510 may include, for example, a thin film transistor (not shown) formed on a substrate (not shown) and a first field generating electrode (not shown) connected thereto. , the second display panel 520 may include, for example, a color filter (not shown) and a second field-generating electrode (not shown) formed on a substrate (not shown). However, without being limited to this, the first display panel 510 may include a color filter, and the first electric field generating electrode and the second electric field generating electrode may be arranged together on the first display panel 510 .

Liquid crystal layer 530 may include a plurality of liquid crystal molecules. Liquid crystal molecules can have either positive or negative dielectric anisotropy. When the liquid crystal molecules have a positive dielectric anisotropy, their long axes are oriented almost parallel to the surfaces of the first display panel 510 and the second display panel 520 in the absence of an electric field. It can be oriented such that its long axis is almost perpendicular to the surfaces of the first display panel 510 and the second display panel 520 in the applied state. On the contrary, when the liquid crystal molecules have negative dielectric anisotropy, their long axes are oriented almost perpendicularly to the surfaces of the first display panel 510 and the second display panel 520 in the absence of an electric field. , its long axis can be oriented almost parallel to the surfaces of the first display panel 510 and the second display panel 520 under the applied electric field.

Although the optical film 100 is positioned outside the liquid crystal display panel 500 and is shown in the drawing to be formed on the lower and upper portions of the liquid crystal display panel 500 , the present invention is not limited thereto, and may be positioned on either of the lower portion and the upper portion of the liquid crystal display panel 500 . Only one of them can be formed.

[EXAMPLES] Hereafter, embodiment of this invention is described in detail through an Example. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Examples 1 to 20: Synthesis of Monomers Example 1: Synthesis of Compound M-1 Compound M-1 is produced according to the following Reaction Scheme M-1 to produce intermediate I-1 and final product compound M-1. The method is divided into steps 1 and 2 and detailed below:

Step 1: Synthesis of intermediate I-1 (2,5-Dihydroxybenzoic acid benzoyl ester):
2,5-Dihydroxybenzoic acid (m=77.06 gr, 0.5 mol, mw=154.13 g/mol), benzylbromide (m=85.52 gr, 0.5 mol) , mw = 171.04 g/mol) and potassium hydrogen carbonate (m = 100.12 gr, 1 mol, mw = 100.12 g/mol) were placed in 0.5 L of dimethylacetamide (DMAC) in a nitrogen atmosphere. Stir at 65° C. for 24 hours. After the reaction is completed, the mixture is added to 3 L of water and stirred. The substance is oily at the beginning of the reaction, but gradually solidifies. After that, the solid was filtered and washed, and then dried under vacuum at 80° C. to obtain intermediate I-1 (m=119.7 gr, 0.49 mol, mw=244.25 g/mol) as a pale yellow powder. (Yield: 98.0%).

_Rf = 0.60 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.37 (s, 2H), 6.83 (d, 1H, J = ^9Hz ), 6.99 (dd, 1H, J = ^9Hz , J = 3.0 Hz), 7.19 ⁽ d, 1H, J = 3.0 Hz), ^7.35-7.50 (m, 5H), 9.25 (br s, 1H, OH), 9.89 (br s, 1H, OH).

Step 2: Synthesis of Monomer M-1 (Bis-trimellitic acid anhydride ester of benzyl-2,5-dihydroxy-benzoate):
After dissolving trimellitic anhydride chloride (m=115.8 gr, 0.55 mol, mw=210.57 g/mol) in 1.5 L of acetonitrile at 100° C., the intermediate was added to the solution. I-1 (m=61.06 gr, 0.25 mol, mw=244.2 g/mol) is added. A solution of triethylamine (m=55.65 gr, 0.55 mol, mw=101.19 g/mol) dissolved in 200 mL of acetonitrile is added dropwise to the reaction mixture at 100° C. and stirred vigorously for 30 minutes. Then, the resulting product is refluxed for 4 hours to remove insoluble substances, filtered at a high temperature, and cooled to room temperature to obtain a white crystalline precipitate. After filtering the precipitate and washing with a small amount of acetonitrile, to the resulting white solid was added 1.5 L of acetic anhydride (m=102.09 gr, 1 mol, mw=102.09 g/mol). Recrystallize twice from acetonitrile. After washing the crystallized solid with a small amount of acetonitrile, it was dried at 90° C. under vacuum for 24 hours to give monomer M-1 (m=118.5 gr, 0.2 mmol, mw=592.48 g/mol). Obtained as a white crystalline solid (yield: 80%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.21 (s, 2H), 7.20-7.30 (m, 5H), 7.67 (d, 1H, J ¹² =8. 7Hz), 7.85 (dd, 1H, J12 = ^8.7Hz , J13 = ^2.7Hz ), 8.14 (d, 1H, J13 = ^2.7Hz ), 8.24 (dd, 1H, J = 8.1 Hz, J = 0.6 Hz), ^{8.30 (} d, 1H, J = 8.1 Hz), ^8.46-8.47 (m, 1H), 8.55 (dd, 1H, J = ^8.1 Hz, J = 1.5 Hz), ^8.65-8.68 (m, 2H);
HRMS APCI (m/z) for _C32H16O12 : _592.0607 (measured mass), _592.0643 (calculated mass) for [M] ⁺ ;
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (268°C);
DSC (heating 10° C./min, N ₂ atmosphere): mp=105.1° C. (CrN), 195.5° C. (NI).

Example 2 Synthesis of Monomer M-2 Compound M-2 was prepared according to Reaction Scheme M-2 below, and the method for preparing intermediates I-2a and I-2b and the final product compound M-2 was performed in step 1, respectively. ~ Step 3 is detailed below:

Step 1: Synthesis of intermediate I-2a (2,5-Dihydroxybenzoic acid 4-bromobenzoyl ester):
2,5-Dihydroxybenzoic acid (mw = 154.13 g/mol, v = 101 mmol, m = 15.57 gr), 1-bromo-4-bromomethylbenzene (1-bromo-4 -bromomethylbenzene (mw=249.93 g/mol, v=101 mmol, m=25.25 gr) and potassium hydrogen carbonate (mw=100.12 g/mol, v=303 mmol, m=30.35 gr) was added to 150 mL of dimethylacetamide (DMAC) and stirred at 65° C. for 24 hours under a nitrogen atmosphere. After the reaction is completed, the mixture is added to 2 L of water and stirred vigorously. After filtering the precipitate, it is thoroughly washed with water. Then, it was dried under reduced pressure at 80° C. for 24 hours to obtain intermediate I-2a (mw=323.15 g/mol, v=99.4 mmol, m=32.13 gr) in the form of a white powder. rate: 98.4%).

R _f =0.4 (eluent ethylacetate:hexane=1:4, TLC silica gel 60 F ₂₅₄ );
¹ H NMR (DMSO-d6) 300 MHz, δ, ppm: 5.33 (s, 2H), 6.83 (d, 1H, J = ⁹ Hz), 6.98 (dd, 1H, J = ⁹ Hz, J13 = 3.0 Hz), 7.17 ⁽ d, 1H, J13 = 3.0 Hz), 7.45 ⁽ d, 2H, ^J12 = 8.4 Hz), 7.62 (d, 2H, ^J12 = 8.4 Hz), 9.20 (s, 1H, OH), 9.89 (s, 1H, OH).

Step 2: Synthesis of intermediate I-2b (2,5-Dihydroxybenzoic acid 4-(phenylethynyl) benzyl ester):
2,5-Dihydroxy-benzoic acid 4-bromobenzyl ester (m=45.24 gr, 140 mmol, mw=323.15 g/mol) and phenylacetylene ( m = 21.45 gr, 210 mmol, mw = 102.13 g/mol) in a mixed solvent of 0.3 L triethylamine and 0.3 L dimethylacetamide in a 1 L 3-neck round bottom flask equipped with a nitrogen inlet and condenser. Dissolve in The solution was stirred and purged with dry nitrogen gas for 1 hour. Then, palladium (II) chloride (m = 0.75 gr, 4.2 mmol, mw = 177.33 g/mol), copper (I) iodide ( Stir while adding m=1.6 gr, 8.4 mol, mw=190.45 g/mol) and triphenylphosphine (m=4.77 gr, 18.3 mol, mw=262.45 g/mol). After that, nitrogen gas is flowed for an additional 10 minutes, the nitrogen outlet is closed, and the mixture is maintained with stirring at 90° C. for 24 hours under a nitrogen atmosphere. After the reaction is finished, triethylamine is evaporated under reduced pressure to obtain the crude product as a brown solid. The crude product is washed with water, dissolved in 1.5 L of hot methanol, then treated with charcoal and filtered. After evaporating the methanol under reduced pressure, the solid obtained is crystallized three times from iso-propanol. Then, it was dried under vacuum at 75° C. for 24 hours to obtain intermediate I-2b (m=25 gr, 72.6 mmol, mw=344.37 g/mol) as a light brown powder (yield: 51 .9%).

_Rf = 0.59 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
¹ H NMR (DMSO _- d6) 300 MHz, δ, ppm: 5.41 (s, 2H), 6.83 (d, 1H, J = ⁹ Hz), 6.99 (dd, 1H, J = ⁹ Hz , J ¹³ = 3.0 Hz), 7.20 (d, 1H, J ¹³ = 3.0 Hz), 7.42-7.45 (m, 3H), 7.51-7.63 (m, 6H) , 9.22 (s, 1H, OH), 9.91 (s, 1H, OH).

Step 3: Synthesis of Monomer M-2 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-(phenylethynyl) benzyl ester):
To 800 mL of acetonitrile was added trimellitic anhydride chloride (m=30.2 gr, 143.4 mmol, mw=210.57 g/mol), intermediate I-2b (m=22.45 gr, 65.2 mmol, mw = 344.32 g/mol), and triethylamine (m = 14.5 gr, 143.4 mol, mw = 101.19 g/mol) were added and reacted in a similar manner to monomer M-1. -2 is synthesized. The reactant was recrystallized twice with acetonitrile while adding acetic anhydride, and the crystallized solid was washed with a small amount of acetonitrile and dried under vacuum at 90° C. for 24 hours. Monomer M-2 (m= 36.4 gr, 52.6 mmol, mw=692.60 g/mol) was obtained as a white solid (yield: 80.6%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.23 (s, 2H), 7.29 (s, 4H), 7.44-7.47 (m, 3H), 7.53- 7.58 (m, 2H), 7.65 (d, 1H, J12 = ^8.7Hz ), 7.86 (dd, 1H, J12 = ^8.7Hz , J13 = ^2.7Hz ), 8. 16 (d, 1H, J13 = ^2.7Hz ), 8.22 (d, 1H, J12 = ^8.4Hz ), 8.30 (d, 1H, J12 = ^8.4Hz ), 8.38 ( s, 1H), 8.50 (dd, 1H, J = ^7.8Hz , J = ^1.5Hz ), 8.65-8.69 (m, 2H);
HRMS APCI (m/z) for _C40H20O12 : _692.0899 (measured mass), _692.0955 (calculated mass) for [M] ^<+> . ;
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (301°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 249.8°C.

Example 3: Synthesis of Monomer M-3 Compound M-3 was prepared according to the following Reaction Scheme M-3, and the method for preparing intermediate I-3 and final product compound M-3 was step 1 and step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-3 (2,5-Dihydroxybenzoic acid 4-fluorobenzoyl ester):
2,5-dihydroxybenzoic acid (m = 17.94 gr, 116.4 mmol, mw = 154.13 g/mol), 4-fluorobenzyl bromide (4- fluorobenzoylbromide) (m = 22 gr, 116.4 mmol, mw = 189.02 g/mol) and potassium hydrogen carbonate (m = 24 gr, 240 mol, mw = 100.12 g/mol) were added and reacted at 65°C for 24 hours under a nitrogen atmosphere. and intermediate I-3 (m = 29.63 gr, 113 mmol, mw = 262.24 g/mol) was obtained in the form of a white solid (yield: 97.1%).

_Rf = 0.58 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.35 (s, 2H), 6.83 (d, 1H, J = ^9Hz ), 6.98 (dd, 1H, J = ^9Hz , J = 3.0 Hz), 7.16 ⁽ d, 1H, J = 3.0 Hz), ^7.22-7.28 (m, 2H), 7.52-7.57 (m, 2H) , 9.19 (s, 1H, OH), 9.92 (s, 1H, OH).

Step 2: Synthesis of Monomer M-3 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-fluorobenzoyl ester):
Trimellitic anhydride chloride (m=51.2 gr, 243 mmol, mw=210.57 g/mol), intermediate I-3 (m=28.97 gr, 110.47 mmol, mw=2) in 800 mL of acetonitrile. 262.24 g/mol), and triethylamine (m=24.55 gr, 243 mol, mw=101.19 g/mol) were added to synthesize the product in a similar manner to monomer M-1, and then acetic acid was added to the product. After recrystallization twice with acetonitrile while adding anhydride, the crystallized solid was washed with a small amount of acetonitrile and dried under vacuum at 90° C. for 24 hours to give monomer M-3 (m=35 gr, 57.3 mmol). , mw=610.47 g/mol) was obtained as a white solid (yield: 51.9%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.19 (s, 2H), 6.99-7.04 (m, 2H), 7.29-7.33 (m, 2H), 7.66 (d, 1H, J12 = ^9Hz ), 7.85 (dd, 1H, J12 = ^8.7Hz , J13 = 3Hz), 8.13 ⁽ d, 1H, J13 = ^2.7Hz ) , 8.24 (d, 1H, J = 8.1 Hz), ^8.30 (d, 1H, J = 8.1 Hz), ^8.43-8.44 (m, 1H), 8.52 ( dd, 1H, J = ^8.1 Hz, J = 1.5 Hz), ^8.65-8.67 (m, 2H);
HRMS APCI (m/z) for _C32H15FO12 : _610.0507 (measured mass), _610.0548 (calculated mass) for [M] ^<+> . ;
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (281°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 219.9°C.

Example 4: Synthesis of Monomer M-4 Compound M-4 was prepared according to Reaction Scheme M-4 below, and the method for preparing intermediates I-2a and I-4 and the final product compound M-4 was performed in Step 1, respectively. ~ Step 3 is detailed below:

Step 1: Synthesis of intermediate I-2a (2,5-Dihydroxybenzoic acid 4-bromobenzoyl ester):
Intermediate I-2a was synthesized in a manner similar to step 1 of Synthesis Example 2.

Step 2: Synthesis of intermediate I-4 (2,5-Dihydroxybenzoic acid 4-(4-phenylethynyl-phenylethynyl) benzyl ester):
Intermediate I-2a (m=32 gr, 99 mmol, mw=323.15 g/mol) and 1-ethynyl-4-phenylethynylbenzene (m=20.63 gr, 102 mmol, mw= 202.26 g/mol) was placed in 0.5 L of triethylamine and dissolved in a 1 L 3-neck round bottom flask equipped with a nitrogen inlet and condenser.

The solution was stirred and purged with dry nitrogen gas for 1 hour. Then, palladium (II) chloride (m = 0.35 gr, 2 mmol, mw = 177.33 g/mol), copper (I) iodide (m = 0.76 gr, 4 mmol, mw=190.45 g/mol) and triphenylphosphine (m=2.1 gr, 8 mmol, mw=262.45 g/mol) are added. After that, nitrogen gas is flowed for an additional 10 minutes, the nitrogen outlet is closed, and the mixture is maintained with stirring at 80° C. for 24 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was evaporated under reduced pressure to obtain the crude product as a brown solid. The crude product is suspended in 400 mL of methanol, boiled for 30 minutes, allowed to cool to room temperature and the solid formed is purified by filtration. The above process is repeated 3 times. The first mother liquor is bright brown with some sediment, the second mother liquor is light brown with a small amount of sediment, and the third mother liquor is pale yellow. The mother liquor produced in the three purification steps was then removed to obtain a product in the form of a light brown powder, which was dried under vacuum at 75° C. for 24 hours to give intermediate I-4 (m=32 .1 gr, 72.2 mmol, mw=444.49 g/mol) was obtained in the form of a light brown powder (yield: 73.0%).

_Rf = 0.59 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.41 (s, 2H), 6.82 (d, 1H, J = ^9Hz ), 6.97 (dd, 1H, J = ^9Hz , J ¹³ = 3.0 Hz), 7.20 (d, 1H, J ¹³ = 3.0 Hz), 7.44-7.46 (m, 3H), 7.53-7.65 (m, 10H) , 9.23 (s, 1H, OH), 9.91 (s, 1H, OH).

Step 3: Synthesis of Monomer M-4 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-(4-phenylethynyl-phenylethynyl) benzyl ester):
Trimellitic anhydride chloride (m=12.5 gr, 59.4 mmol, mw=210.57 g/mol), intermediate I-4 (m=12 gr, 27 mmol, mw=444.5 g/mol) in 800 mL of acetonitrile. 49 g/mol) and triethylamine (m=6 gr, 59.4 mol, mw=101.19 g/mol) are added and reacted to synthesize monomer M-4 in a similar manner to monomer M-1. After the reaction was completed, the product was recrystallized twice with acetonitrile while adding acetic anhydride, and the crystallized solid was washed with a small amount of acetonitrile and dried under vacuum at 90° C. for 24 hours. , the monomer M-4 (m=15.1 gr, 19 mmol, mw=792.72 g/mol) was obtained as a brownish solid (yield: 70.4%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.23 (s, 2H), 7.30 (s, 4H), 7.44-7.47 (m, 3H), 7.58- 7.67 (m, 7H), 7.86 (dd, 1H, J12 = ^8.7Hz , J13 = ^2.7Hz ), 8.18 (d, 1H, J13 = ^2.7Hz ), 8. 23 (d, 1H, J12 = ^7.8Hz ), 8.30 (d, 1H, J12 = ^8.1Hz ), 8.37 (s, 1H), 8.50 (dd, 1H, ^J12 = 7.8 Hz, J=0.9 Hz), 8.66-8.69 (m, 2H);
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (261°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 254.7°C.

Example 5: Synthesis of Monomer M-5 Compound M-5 was prepared according to Reaction Scheme M-5 below, and the method for preparing intermediate I-5 and final product compound M-5 was step 1 and step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-5 (2,5-Dihydroxy-benzoic acid 4-phenylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (m=15.41 gr, 100 mmol, mw=154.12 g/mol), 4-chloromethyl-N- Phenyl-benzamide (4-chloromethyl-N-phenyl-benzamide) (m = 24.57 gr, 100 mmol, mw = 245.71 g/mol) and potassium hydrogen carbonate (m = 30 gr, 300 mmol, mw = 100.12 g/mol ) and reacted at 65° C. for 24 hours under a nitrogen atmosphere to synthesize a product in a similar manner to intermediate I-1, and then crystallize with acetone/iso-propanol to obtain intermediate I-5 (m=27 .3 gr, 75 mmol, mw=363.37 g/mol) was obtained as a white solid (yield: 75.0%).

R _f =0.75 (eluent ethylacetate:hexane=1:1, TLC silica gel 60 F ₂₅₄ );
¹ H NMR (DMSO _- d6) 300 MHz, δ, ppm: 5.46 (s, 2H), 6.84 (d, 1H, J = ⁹ Hz), 6.99 (dd, 1H, J = ⁹ Hz , J = 3.0 Hz), ^7.08-7.13 (m, 1H), 7.21 (d, 1H, J = 3.0 Hz), ^7.33-7.38 (m, 2H) , 7.63 (d, 2H, ^J12 = 8.4 Hz), 7.78 (d, 2H, J12 = 7.8 Hz), 7.99 (d, 2H, ^J12 = 8.4 Hz), ⁹ .23 (s, 1H, OH), 9.90 (s, 1H, OH), 10.27 (s, 1H, NH).

Step 2: Synthesis of Monomer M-5 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-phenylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (m=24.2 gr, 114.9 mmol, mw=210.57 g/mol), intermediate I-5 (m=19 gr, 52.2 mmol, mw=2) in 1 L of acetonitrile. 363.37 g/mol) and triethylamine (m=11.6 gr, 114.9 mol, mw=101.19 g/mol) are added and reacted to synthesize monomer M-5 in a similar manner to monomer M-1. . After the reaction is completed, the product is crystallized twice with acetonitrile while adding acetic anhydride, and the crystallized solid is washed with a small amount of acetonitrile and dried under vacuum at 90° C. for 24 hours to give a monomer. M-5 (m=26.3 gr, 37 mmol, mw=711.60 g/mol) was obtained as a white solid (yield: 70.9%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.30 (s, 2H), 7.09-7.14 (m, 1H), 7.33-7.43 (m, 4H), 7.66 (d, 1H, J = ^9Hz ), 7.71-7.76 (m, 4H), 7.86 (dd, 1H, J = ^9Hz , J = 3Hz), ^8.18- 8.20 (m, 2H), 8.30 (d, 1H, J12 = ^8.1Hz ), 8.41 (s, 1H), 8.49 (dd, 1H, J12 = ^8.1Hz , J = 1.5 Hz), 8.66-8.69 (m, 2H);
HRMS APCI (m/z) for _C39H21NO13 : _{712.1098 (} measured mass), 712.1091 (calculated mass) for [M+H] ^<+ >. ;
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (304°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 259°C.

Example 6: Synthesis of Monomer M-6 Compound M-6 was prepared according to Reaction Scheme M-6 below, and the method for preparing intermediate I-6 and final product compound M-6 was step 1 and step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-6 (2,5-Dihydroxy-benzoic acid 4-(4-phenylethynylphenylcarbonyl) benzoyl ester):
2,5-dihydroxybenzoic acid (m=13.6 gr, 88.1 mmol, mw=154.12 g/mol), 4-chloromethylbenzoic acid 4- in 0.3 L of dimethylacetamide 4-chloromethylbenzoic acid 4-phenylethynylphenyl ester (m=30.55 gr, 88.1 mmol, mw=316.82 g/mol) and potassium hydrogen carbonate (m=26.5 gr, 264.3 mmol, mw = 100.12 g/mol) and reacted at 65°C for 24 hours under a nitrogen atmosphere to synthesize intermediate I-6 in a similar manner to intermediate I-1. The product was crystallized with acetone/iso-propanol to give intermediate I-6 (m=27.9 gr, 60 mmol, mw=464.48 g/mol) as a white solid (yield: 68.1 %).

¹ H NMR (DMSO _- d6) 300 MHz, δ, ppm: 5.50 (s, 2H), 6.85 (d, 1H, J = ^9Hz ), 7.00 (dd, 1H, J = ^9Hz ) , J = 3.0 Hz), 7.23 ⁽ d, 1H, J = 3.0 Hz), ^7.36-7.46 (m, 5H), 7.56-7.60 (m, 2H) , 7.65-7.74 (m, 4H), 8.15-8.20 (m, 2H), 9.23 (s, 1H, OH), 9.89 (s, 1H, OH).

Step 2: Synthesis of Monomer M-6 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-(4-phenylethynylphenoxycarbonyl) benzyl ester):
Trimellitic anhydride chloride (m=22.6 gr, 107.5 mmol, mw=210.57 g/mol), intermediate I-6 (m=22.7 gr, 48.9 mmol, mw = 464.48 g/mol) and triethylamine (m = 10.9 gr, 107.5 mol, mw = 101.19 g/mol) were added and reacted to give monomer M-6 in a similar manner to monomer M-1. Synthesize. After the reaction is completed, the product is crystallized twice with acetonitrile while adding acetic anhydride, and the crystallized solid is washed with a small amount of acetonitrile and dried under vacuum at 90° C. for 24 hours to give a monomer. M-6 (m=24.6 gr, 30.3 mmol, mw=812.71 g/mol) was obtained as a white solid (yield: 62.0%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.33 (s, 2H), 7.37-7.68 (m, 11H), 7.87-7.93 (m, 3H), 8.19-8.30 (m, 3H), 8.42 (br s, 1H), 8.53 (br s, 1H), 8.67 (br s, 1H).

Example 7: Synthesis of Monomer M-7 Compound M-7 was prepared according to Reaction Scheme M-7 below, and the method for preparing intermediate I-7 and final product compound M-7 was step 1 and step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-7 (2,5-Dihydroxybenzoic acid 4-tert-butylbenzoyl ester):
2,5-dihydroxybenzoic acid (m=33.72 gr, 218.81 mmol, mw=154.12 g/mol), 4-tert-butylbenzyl bromide ( 4-tert-butylbenzyl bromide) (m=26.95 gr, 218.81 mmol, mw=227.14 g/mol) and potassium hydrogen carbonate (m=43.81 gr, 437.62 mmol, mw=100.12 g/mol) and reacted at 65° C. for 24 hours under a nitrogen atmosphere to synthesize intermediate I-7 (m=65 gr, 216.41 mmol, mw=300.36 g/mol) in a similar manner to intermediate I-1. The intermediate I-7 was a yellow solidified oil at low temperature (yield: 98.9%).

_Rf = 0.79 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 1.28 (s, 9H), 5.32 (s, 2H), 6.83 (d, 1H, J = 9.0 Hz), ⁶ .97 (dd, 1H, J = ^9.0Hz , J = ^3.0Hz ), 7.18 (d, 1H, J = ^3.0Hz ), 7.38-7.45 (m, 4H) , 9.60 (br s, 2H).

Step 2: Synthesis of Monomer M-7 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-tert-butylbenzoyl ester):
Trimellitic anhydride chloride (m=99 gr, 470 mmol, mw=210.57 g/mol), intermediate I-7 (m=65.7 gr, 218.7 mmol, mw=2) in 1.5 L of acetonitrile. 300.36 g/mol), and triethylamine (m=47.5 gr, 470 mmol, mw=101.19 g/mol), in a similar manner to monomer M-1 above, to prepare a monomer M-7 solution. to synthesize. If the solution is filtered hot to remove insoluble matter, the reaction product, which is poorly soluble in acetonitrile, immediately precipitates. This is treated twice with acetic anhydride (50 mL) dissolved in acetonitrile (800 mL) under reflux conditions for 2 hours. The resulting solid was cooled to room temperature, filtered, washed with a small amount of acetonitrile, dried under vacuum at 90° C. for 24 hours, and monomer M-7 (m=96.6 gr, 148.9 mmol, mw=648 .59 g/mol) was obtained as a white solid (yield: 68.1%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 1.22 (s, 9H), 5.17 (s, 2H), 7.20 (d, 2H, J = 8.4 Hz), ^{7 .27 (} d, 2H, ^J12 = 8.4 Hz), 7.67 (d, 1H, J12 = 8.7 Hz), 7.85 (dd, 1H, J12 = 8.7 Hz, J13 = ² .7Hz), 8.12 (d, 1H, J13 = ^2.7Hz ), 8.24 (dd, 1H, J12 = ^7.5Hz , J14 = ^1.2Hz ), 8.29 (d, 1H , J ¹² =8.4 Hz), 8.53-8.59 (m, 1H), 8.64-8.68 (m, 1H);
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (305.5°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 234.7°C.

Example 8: Synthesis of Monomer M-8 Compound M-8 was prepared according to Reaction Scheme M-8 below, and the process for preparing intermediate I-8 and final product compound M-8 was step 1 and step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-8 (3,5-Dihydroxybenzoic acid 4-tert-butylbenzoyl ester):
3,5-dihydroxybenzoic acid (m = 15.41 gr, 0.1 mol, mw = 154.12 g/mol), 4-tert-butylbenzyl bromide (4- tert-butylbenzoyl bromide) (m = 22.71 gr, 0.1 mol, mw = 227.14 g/mol) and potassium hydrogen carbonate (m = 20.804 gr, 0.2 mol, mw = 100.12 g/mol). , under a nitrogen atmosphere at 65° C. for 24 hours to give intermediate I-8 (m=57.7 gr, 0.192 mol, mw=300.36 g/mol) in a similar manner to intermediate I-1 as a white solid. Obtained in solid state (yield: 96.0%).

_Rf = 0.38 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
mp = 186-188°C;
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 1.28 (s, 9H), 5.24 (s, 2H), 6.43 (t, 1H, J = 2.4 Hz), ⁶ .84 (d, 2H, J ¹³ =2.4 Hz), 7.34-7.44 (m, 4H), 9.65 (br s, 2H).

Step 2: Synthesis of Monomer M-8 (Bis-trimellitic acid anhydride ester of 3,5-dihydroxybenzoic acid 4-tert-butylbenzoyl ester):
Trimellitic anhydride chloride (m=23.16 gr, 110 mmol, mw=210.57 g/mol), intermediate I-8 (m=15.01 gr, 50 mmol, mw=2) in 0.5 L of acetonitrile. 300.36 g/mol), and triethylamine (m=11.11 gr, 110 mol, mw=101.19 g/mol) were added and reacted in a similar manner to the monomer M-1. Prepare a solution of M-8. The solution was filtered hot to remove insoluble substances, concentrated to 250 mL, and stored in a refrigerator for 48 hours.

The resulting solid was filtered and crystallized twice with acetonitrile (200 mL) while adding acetic anhydride (10 mL) to give the product. The product was dried under vacuum at 80° C. for 24 hours to give monomer M-8 (m=18.34 gr, 28.3 mmol, mw=648.59 g/mol) as a white solid (yield: 56 .6%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 1.27 (s, 9H), 5.37 (s, 2H), 7.43 (s, 4H), 7.88 (t, 1H, J = 2.1 Hz), 8.04 ⁽ d, 2H, J = 2.1 Hz), 8.29 (d, 2H, J = ^8.1 Hz), ^8.63-8.67 (m, 4H);
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (316.4°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 212.6°C.

Example 9: Synthesis of Monomer M-9 Compound M-9 was prepared according to Reaction Scheme M-9 below, and the method for preparing intermediates I-9a and I-9b and the final product Compound M-9 was respectively performed in Step 1. ~ Step 3 is detailed below:

Step 1: Synthesis of intermediate I-9a (3,5-Dihydroxybenzoic acid 4-bromobenzoyl ester):
3,5-Dihydroxybenzoic acid (m = 47.68 gr, 309.4 mmol, mw = 154.13 g/mol), 1-bromo-4-bromomethylbenzene (1-bromo-4 -bromomethylbenzene) (m=77.32 gr, 309.4 mmol, mw=249.93 g/mol) and potassium hydrogen carbonate (m=62.1 gr, 620 mmol, mw=100.12 g/mol) in 500 Ml of dimethylacetamide. and stirred at 65° C. for 24 hours under nitrogen atmosphere. After the reaction was completed, the reactant was poured into a 2 L container and vigorously stirred. The resulting precipitate was filtered, washed thoroughly with water, and dried under reduced pressure at 80° C. for 24 hours to give intermediate I-9a (m=98 gr, 303.3 mmol, mw=323.15 g/mol). It was obtained as a white powder (yield: 98.0%).

R _f =0.27 (eluent ethylacetate:hexane=1:2, TLC silica gel 60 F ₂₅₄ );
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.26 (s, 2H), 6.45 (dd, 1H, J ¹³ =2.1 Hz), 6.84 (d, 2H, J ¹³ = 2.1 Hz), 7.40 (d, 2H, ^J12 = 8.4 Hz), 7.61 (d, 2H, ^J12 = 8.4 Hz), 9.65 (s, 2H, OH).

Step 2: Synthesis of intermediate I-9b (3,5-Dihydroxybenzoic acid 4-(4-phenylethynyl-phenylethynyl) benzyl ester):
Intermediate I-9a (m=48.47 gr, 150 mmol, mw=323.15 g/mol) and 1-ethynyl-4-phenylethynylbenzene (m=30.34 gr, 150 mmol, mw = 202.26 g/mol) was placed in 600 Ml of triethylamine/dimethylacetamide 1:1 mixed solvent and dissolved in a 1 L 3-neck round bottom flask equipped with nitrogen inlet and condenser. After the solution was stirred and purged with dry nitrogen gas for 1 hour, palladium(II) chloride (m=0.8 gr, 4.5 mmol, mw=177.33 g/mol), copper(I)iodide (m=1.71 gr, 9 mmol, mw=190.45 g/mol) and triphenylphosphine (m=4.72 gr, 18 mmol, mw=262.45 g/mol ) was added. After that, nitrogen gas was flowed for an additional 10 minutes, the nitrogen outlet was closed, and the mixture was maintained under stirring at 80° C. for 24 hours under a nitrogen atmosphere. After the reaction was completed, triethylamine was evaporated under reduced pressure and the resulting solution was added to 2 L of water to obtain a brown solid. It was filtered and washed with water and the product obtained was purified by suspending it in 500 mL of DCM, boiling for 30 minutes and then filtering the solid formed after cooling to room temperature. The above process was repeated three times. The first mother liquor was bright brown with some sediment, the second mother liquor was light brown with a small amount of sediment, and the third mother liquor was pale yellow. The mother liquor generated in the three purification steps was then removed to obtain a product in the form of a light brown powder, which was dried under vacuum at 75° C. for 24 hours to obtain intermediate I-9b (m=30 gr, 67.5 mmol, mw=444.49 g/mol) was obtained in the form of a light brown powder (yield: 45.0%).

_Rf = 0.72 (eluent ethylacetate: hexane = 1:1, TLC silica gel 60 _F254 );
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.34 (s, 2H), 6.45 (dd, 1H, J ¹³ =2.1 Hz), 6.87 (d, 2H, J ¹³ = 2.1 Hz), 7.43-7.64 (m, 13H), 9.66 (s, 2H, OH).

Step 3: Synthesis of Monomer M-9 (Bis-trimellitic acid anhydride ester of 3,5-dihydroxybenzoic acid 4-(4-phenylethynyl-phenylethynyl) benzyl ester):
Trimellitic anhydride chloride (m=30.4 gr, 144.8 mmol, mw=210.57 g/mol), intermediate I-9b (m=29.25 gr, 65.5 g/mol) in 1.5 L of acetonitrile. 8 mmol, mw = 444.49 g/mol) and triethylamine (m = 14.62 gr, 144.8 mol, mw = 101.19 g/mol) were added and reacted in a similar manner to the monomer M-1. After preparing the M-9 solution, the solution was filtered at hot conditions with the addition of charcoal. A solid precipitates after cooling to room temperature. The product, which is poorly soluble in acetonitrile, was purified by suspending it in 500 mL of acetonitrile and 20 mL of acetic anhydride, boiling for 2 hours and filtering the solid that formed after cooling to room temperature. The above process was repeated twice. The crystallized solid was washed with a small amount of acetonitrile and then dried under vacuum at 75° C. for 24 hours to give monomer M-9 (m=32 gr, 40.4 mmol, mw=792.72 g/mol) as a yellow solid. obtained (yield: 61.3%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.46 (s, 2H), 7.44-7.47 (m, 3H), 7.56-7.64 (m, 10H), 7.91 ⁽ dd, 1H, J13 = 2.1 Hz), 8.08 ⁽ d, 2H, J13 = 2.1 Hz), 8.29 (d, 2H, J12 = 8.4 Hz), ⁸ . 62-8.68 (m, 4H);
HRMS APCI (m/z) for _C48H24O12 : _712.1197 (measured mass), _792.1268 (calculated mass) for [M] ^<+> . ;
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (316°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 225°C.

Example 10: Synthesis of Monomer M-10 Compound M-10 was prepared according to Reaction Scheme M-10 below, and the method for preparing intermediate I-10 and final product compound M-10 was step 1 and step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-10 (3,5-Dihydroxybenzoic acid benzoyl ester):
3,5-dihydroxybenzoic acid (m=31.44 gr, 0.2 mol, mw=154.12 g/mol), benzyl bromide in 0.3 L of dimethylacetamide (DMAC) ) (m = 34.2 gr, 0.2 mol, mw = 171.04 g/mol) and potassium bicarbonate (m = 40 gr, 0.4 mol, mw = 100.12 g/mol) were added and heated at 65°C under a nitrogen atmosphere. After reacting for 24 hours and synthesizing a product in a similar manner to intermediate I-1, the mixture was added to 1 L of water, and the precipitated oily substance was extracted as ethyl acetate. The ethyl acetate solution was washed with 3% aqueous hydrochloric acid and water, and then dried over anhydrous magnesium sulfate. Evaporation of the solvent under reduced pressure gave a solid which was dried under vacuum at 100° C. to give intermediate I-10 (m=48 gr, 196.52 mmol, mw=244.24 g/mol) as a white solid. (Yield: 98.3%).

_Rf = 0.34 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
mp = 130-132°C;
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.29 (s, 2H), 6.44 (t, 1H, J ¹³ =2.4 Hz), 6.85 (d, 2H, J ¹³ = 2.4 Hz), 7.33-7.47 (m, 5H), 9.64 (s, 2H).

Step 2: Synthesis of Monomer M-10 (Bis-trimellitic acid anhydride ester of 3,5-dihydroxybenzoic acid benzyl ester):
Trimellitic anhydride chloride (m=55.6 gr, 264 mmol, mw=210.57 g/mol), intermediate I-10 (m=30 gr, 122.8 mmol, mw=2) in 0.8 L of acetonitrile. 244.24 g/mol) and triethylamine (m=26.7 gr, 264 mmol, mw=101.19 g/mol) are added and reacted in a similar manner to monomer M-1 to synthesize monomer M-10. The resulting solution was filtered under hot conditions to remove insoluble materials to obtain an acetonitrile solution in which the product was dissolved. After cooling, the precipitated solid was recrystallized twice with a mixed solvent of acetonitrile (300 mL) and acetic anhydride (20 mL), and then dried under vacuum at 80° C. for 24 hours to give monomer M-10 (m=23 gr, 38. 8 mmol, mw=592.48 g/mol) in the form of a yellow crystalline material (yield: 31.6%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.42 (s, 2H), 7.44-7.53 (m, 5H), 7.90 (t, 1H, J ¹³ =2. 1 Hz), 8.06 ⁽ d, 2H, J = 2.1 Hz), 8.29 (d, 2H, J = 8.4 Hz), ^8.63-8.67 (m, 4H);
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% lossz (197.5°C);
DSC (heating 10° C./min, N ₂ atmosphere): mp to 150° C. (decomposition).

Example 11 Synthesis of Monomer M-11 Compound M-11 was prepared according to the following Reaction Scheme M-11, and the method for preparing intermediate I-11 and the final product compound M-11 was described in steps 1 and 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-11 (2,5-Dihydroxybenzoic acid 2-phenylethyl ester):
2,5-dihydroxybenzoic acid (m=18.14 gr, 117.68 mmol, mw=154.12 g/mol), 2-bromoethylbenzene ( 2-bromoethylbenzene) (m=21.35 gr, 115.37 mol, mw=185.06 g/mol) and potassium hydrogen carbonate (m=23.4 gr, 230.74 mmol, mw=100.12 g/mol), It was reacted in a similar manner to intermediate I-1 at 65° C. for 24 hours under nitrogen atmosphere. When the mixture was added to 1 L of water, the precipitated oily substance gradually solidified to obtain the product. The product was filtered, washed with water and dried at room temperature to give intermediate I-11 (m=27.6gr, 106.86mmol, mw=258.27g/mol) as a pale yellow solid. (Yield: 92.6%).

_Rf = 0.64 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 );
mp = 88-90°C;
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 3.04 (t, 2H, J = ^6.9 Hz), 4.50 (t, 2H, J = 6.9 Hz), ^6.81 (d, 1H, ^J12 = 8.7 Hz), 6.97 ⁽ dd, 1H, ^J12 = 8.7 Hz, J13 = 3.0 Hz), 7.11 ⁽ d, 1H, J13 = 3.0 Hz ), 7.20-7.29 (m, 1H), 7.31-7.33 (m, 4H), 9.22 (s, 1H), 9.37 (s, 1H).

Step 2: Synthesis of Monomer M-11 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 2-phenylethyl ester):
Trimellitic anhydride chloride (m=47.94 gr, 227.7 mmol, mw=210.57 g/mol), intermediate M-17 (m=27.35 gr, 105.5 g/mol) in 0.6 L of acetonitrile. 9 mmol, mw = 258.27 g/mol), and triethylamine (m = 23 gr, 227.7 mmol, mw = 101.19 g/mol) were charged and reacted in a similar manner to monomer M-1 to give monomer M-11. to obtain a solution. The resulting solution was filtered under hot conditions to remove insoluble materials to obtain an acetonitrile solution in which the product was dissolved. After cooling, the precipitated solid was recrystallized twice with a mixed solvent of acetonitrile (300 mL) and acetic anhydride (20 mL), and then dried under vacuum at 80° C. for 24 hours to give monomer M-11 (m=32 gr, 52.0 g). 76 mmol, mw=606.50 g/mol) was obtained in the form of a yellow crystalline substance (yield: 49.8%).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 2.86 (t, 2H, J = 6.9 Hz), ^4.38 (t, 2H, J = 6.9 Hz), ^7.14 -7.27 (m, 5H), 7.67 (d, 1H, J12 = ^8.7Hz ), 7.85 (dd, 1H, J12 = ^8.7Hz , J13 = ^3.0Hz ), 8 .01 (d, 1H, J = 3.0 Hz), ^8.28-8.33 (m, 2H), 8.59-8.69 (m, 4H);
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (189°C);
DSC (heating 10°C/min, N ₂ atmosphere): mp = 117.4°C (decomposition).

Example 12: Synthesis of Monomer M-12 Compound M-12 was prepared according to the following Reaction Scheme M-12, and the method for preparing intermediate I-12 and final product compound M-12 was described in steps 1 and 2, respectively. Separately detailed below:

Step 1: Synthesis of Intermediate I-12 (2,5-Dihydroxybenzoic acid 4-(9H-fluoren-9-yloxycarbonyl)benzoyl ester):
2,5-dihydroxybenzoic acid (m=3154.12 gr, 126.76 mmol, m=19) in 0.2 L of dimethylacetamide (DMAC) in an analogous manner to intermediate I-1. .54 gr), 4-chloromethyl-benzoic acid 9H-fluoren-9-yl ester (mw=334.80 g/mol, 120.73 mmol, m=40 .42 gr), and potassium hydrogen carbonate (mw=100.12 g/mol, 241.46 mmol, m=24.17 gr) are added and reacted at 75° C. for 24 hours under a nitrogen atmosphere to synthesize intermediate I-12. The white solid that precipitated in 1.5 L of water was filtered, washed with water, crystallized under reduced pressure from dimethylchloromethane/isopropanol and dried under reduced pressure at 95° C. for 24 hours to yield the intermediate. I-12 (m=35 gr, mw=452.46 g/mol, 77.35 mmol) was obtained as a white crystalline phase solid (Yield: 64.1%).

_Rf = 0.56 (eluent ethylacetate: hexane = 1:2, TLC silica gel 60 _F254 ).
mp = 200-202°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.44 (s, 2H), 6.83 (d, 1H, J = 8.7 Hz), ^6.97-7.00 (m, 2H), 7.18 ⁽ d, 1H, J13 = 3.0 Hz), 7.35 (td, 2H, ^J12 = 7.5 Hz, J13 = 0.9 Hz), 7.49 ⁽ t, 2H, ^J12 = 7.5 Hz), 7.63 (t, 4H, ^J12 = 8.4 Hz), 7.89 (d, 2H, ^J12 = 7.5 Hz), 8.02 (d, 2H, ^J12 = 8.4 Hz), 9.21 (s, 1H), 9.85 (s, 1H).

Step 2: Synthesis of Monomer M-12 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-(9H-fluoren-9-yloxycarbonyl) benzyl ester):
In 1 L of acetonitrile was added trimellitic anhydride chloride (mw=210.57 g/mol, 101.83 mmol, m=21.44 gr), 2,5-dihydroxybenzoic acid 4-(9H-fluorene-9- yloxycarbonyl) benzyl ester (2,5-dihydroxybenzoic acid 4-(9H-fluoren-9-yloxycarbonyl) benzyl ester) (mw = 452.47 g/mol, 47.36 mmol, m = 21.43 gr), and triethylamine ( Triethylamine) (mw=101.19 g/mol, 101.83 mmol, m=10.30 gr) is added and reacted to synthesize monomer M-12 in a similar manner to monomer M-1. After the reaction is complete, the solution is concentrated to 0.4 L volume. After cooling to ambient temperature a precipitate is formed. The solid is filtered, washed with a small amount of water to remove triethylamine hydrochloride, and dried at 80° C. under reduced pressure. The crude product (Crude material) was recrystallized twice with a mixture of acetonitrile (400 mL) and acetic anhydride (20 mL), and the second time was dried over charcoal at 85° C. under reduced pressure for 24 hours. The product monomer M-12 was obtained as a bright yellow solid (m=14.49 gr, mw=800.70 g/mol, 18.1 mmol), (38.2% yield).

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.27 (s, 2H), 6.93 (s, 1H), 7.32-7.51 (m, 6H), 7.63- 7.66 (m, 3H), 7.77-7.88 (m, 6H), 8.15 (d, 2H, J = ^2.7Hz ), 8.20 (d, 1H, J = ⁸ .1Hz), 8.27 (d, 1H, J = ^8.4Hz ), 8.44 (s, 1H), 8.52 (d, 1H, J = ^7.8Hz ), 8.64-8 .66 (m, 2H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (154.4°C);
DSC (heating 10° C./min, N ₂ atmosphere): mp=170.3° C. (decomp.).

Example 13: Synthesis of Monomer M-13 Compound M-13 was prepared according to the following Reaction Scheme M-13, and the method for preparing intermediate I-13 and final product compound M-13 was described in Step 1 and Step 2, respectively. Separately detailed below:

Step 1: Synthesis of Intermediate I-13 (2,5-Dihydroxybenzoic acid 4-(4-bromobenzyloxycarbonyl) benzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 75.66 mmol, m=11.66 gr), 4- 4-chloromethyl-benzoic acid 4-bromobenzyl ester (mw=339.62 g/mol, 75.66 mmol, m=25.69 gr) and potassium hydrogen carbonate (mw=100. 12 g/mol, 151.32 mmol, m=15.15 gr) was reacted at 70° C. under nitrogen atmosphere for 24 hours to give intermediate I-13 in a similar manner to intermediate I-1. After the reaction is completed, the mixture is put into 1 L of water to produce a white solid, which is filtered, washed with water, crystallized from dichloromethane/methanol and dried at 95° C. under reduced pressure for 24 hours. . The product intermediate I-13 is obtained as a white crystalline solid (90.2% yield). m = 31.2 gr (mw = 457.28 g/mol, 68.23 mmol).

R _f =0.46 (eluent ethylacetate:hexane=1:2, TLC silica gel 60 F ₂₅₄ )
mp = 146-148°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.34 (s, 2H), 5.45 (s, 2H), 6.83 (d, 1H, J = 8.7 Hz), ⁶ .98 ⁽ dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 7.19 ⁽ d, 1H, J13 = 3.0 Hz), 7.44 (d, 2H, J12 = ⁸ .4Hz), 7.59-7.64 (m, 4H), 8.04 (d, 2H, J = ^8.4Hz ), 9.21 (s, 1H), 9.86 (s, 1H) .

Step 2: Synthesis of Monomer M-13 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-(4-bromobenzyloxycarbonyl) benzyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 66.76 mmol, m=14.06 gr), 4-(4-bromobenzyl 2,5-dihydroxybenzoate) in 0.8 L of acetonitrile oxycarbonyl) benzyl ester (2,5-dihydroxybenzoic acid 4-(4-bromobenzyloxycarbonyl) benzyl ester) (mw = 457.28 g/mol, 31.05 mmol, m = 14.20 gr), and trimethylamine (mw = 101.19 g/mol, 66.76 mmol, m=6.74 gr) are added and reacted to obtain monomer M-13 in analogy to monomer M-1. After the reaction is finished, the solution is concentrated to 0.4 L volume. A precipitate is formed when the solution is cooled to room temperature. The solid is filtered, washed with a small amount of water to remove triethylamine hydrochloride and dried at 80° C. under reduced pressure. The crude product (Crude material) is recrystallized from a mixture of acetonitrile (300 mL) and acetic anhydride (20 mL) and dried at 85° C. for 24 hours with a second addition of charcoal. The resulting monomer M-13 is a white solid. m=15.56 gr (mw=805.51 g/mol, 19.32 mmol), yield 62.2%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 5.28 (s, 2H), 5.29 (s, 2H), 7.38-7.45 (m, 4H), 7.61 ( d, 2H, ^J12 = 8.4 Hz), 7.66 (d, 1H, ^J12 = 8.7 Hz), 7.76 (d, 2H, ^J12 = 8.7 Hz), 7.85 (dd, 1H, J = 8.7 Hz, J = 2.7 Hz), ^8.16-8.19 (m, 2H), 8.30 (d, 1H, J = ^8.1 Hz), ^8.39 ( s, 1H), 8.49 (d, 1H, J ¹² =8.1 Hz), 8.65-8.68 (m, 2H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (348.7°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 227.5°C.

Example 14: Synthesis of Monomer M-14 Compound M-14 was prepared according to Reaction Scheme M-14 below, and the process for preparing intermediate I-14 and final product compound M-14 was described in steps 1 and 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-14 (2,5-Dihydroxybenzoic acid 4-hexylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 118.9 mmol, m=18.33 gr) in 0.2 L of dimethylacetamide (DMAC), 4- 4-chloromethyl-N-hexylbenzamide (mw = 253.77 g/mol, 115.5 mol, m = 29.30 gr) and potassium hydrogen carbonate (mw = 100.12 g/mol, 231 mmol, m = 23.13 gr) and reacted at 65°C under nitrogen atmosphere for 24 hours to obtain intermediate I-14 in a similar manner to intermediate I-1.After the reaction was completed, the mixture was A white solid precipitates in 1.5 L of water, which is filtered, washed with water, crystallized from aqueous methanol and dried at 95° C. under reduced pressure for 24 hours.Product Intermediate I-14 is obtained as a white crystalline solid.

_Rf = 0.21 (eluent ethylacetate: hexane = 1:2, TLC silica _gel60F254 ), m = 37.63 gr (mw = 371.43 g/mol, 101.3 mmol), yield 87.7%. mp = 127-128°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.86 (t, 3H, J ¹² =6.9 Hz), 1.25-1.35 (m, 6H), 1.46-1. 56 (m, 2H), 3.24 (dt, J = 6Hz, 6.9Hz), 5.41 (s, 2H), 6.84 (d, 1H, J12 = ^8.7Hz ), 6.98 (dd, 1H, ^J12 = 8.7 Hz, J13 = 3.0 Hz), 7.18 ⁽ d, 1H, J13 = 3.0 Hz), 7.55 ⁽ d, 1H, ^J12 = 8.4 Hz ), 7.86 (d, 1H, J = ^8.4Hz ), 8.46 (t, 1H, J = 6Hz, NH), 9.21 (s, 1H), 9.89 (s, 1H) .

Step 2: Synthesis of Monomer M-14 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-hexylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 216.5 mmol, m=45.59 gr), intermediate I-14 (2,5-dihydroxybenzoic acid 4-hexylcarbamoylbenzoyl ester) in 1 L of acetonitrile ) (mw = 371.43 g/mol, 100.7 mmol, m = 37.40 gr) and triethylamine (mw = 101.19 g/mol, 216.5 mmol, m = 21.87 gr) were added to form monomer M-1 and React in a similar manner to obtain the monomer M-14. The resulting solution is filtered hot to remove insoluble material and concentrated to 0.5 L volume. Water is added to precipitate the crude product, which is filtered, washed with water and air dried. The crude product was recrystallized twice with a mixture of acetonitrile (500 mL) and acetic anhydride (40 mL) and then dried under vacuum at 95° C. for 24 hours to give monomer M-14 as a white crystalline material. m=39 gr (mw=719.66 g/mol, 54.18 mmol), yield: 53.8%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.85-0.90 (m, 3H), 1.29 (br s, 6H), 1.48-1.53 (m, 2H) , ^3.17-3.24 (m, 2H), 5.25 (s, 2H), 7.31 (d, 2H, J = 8.4 Hz), ^7.58 (d, 2H, J = 8.4 Hz), 7.64 (d, 1H, J ¹² =8.7 Hz), 7.85 (dd, 1H, J ¹² =8.7 Hz, J ¹³ =3.0 Hz), 8.12-8. 17 (m, 2H), 8.28-8.35 (m, 3H), 8.44 (dd, 1H, J = 8.1 Hz, J = ^1.2 Hz), ^8.65-8.70 (m, 2H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (309.5°C);
DSC (heating 10°C/min, _N2 atmosphere): mp = 207.2°C.

Example 15: Synthesis of Monomer M-15 Compound M-15 was prepared according to the following Reaction Scheme M-15, and the method for preparing intermediate I-15 and final product compound M-15 was described in steps 1 and 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-15 (2,5-Dihydroxybenzoic acid 4-dodecylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 101.1 mmol, m=15.58 gr), 4-chloromethyl- N-dodecylbenzamide (4-chloromethyl-N-dodecylbenzamide (mw = 337.94 g/mol, 98.15 mol, m = 33.17 gr) and potassium hydrogen carbonate (mw = 100.12 g/mol, 200 mmol, m = 20 .02 gr) and reacted at 65° C. for 24 hours under nitrogen atmosphere to obtain intermediate I-15 in a similar manner to intermediate I-1.After the reaction was completed, the mixture was added to 1.5 L of water. The precipitated white solid was filtered, washed with water, crystallized with 500 mL of methanol, and dried under reduced pressure at 90° C. for 24 hours to obtain intermediate I-15 as a white crystalline solid.

_Rf = 0.24 (eluent ethylacetate: hexane = 1:2, TLC silica _gel60F254 ), m = 34.1 gr (mw = 455.60 g/mol, 74.85 mmol), yield 76.3%.
mp = 122-124°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.82-0.86 (m, 3H), 1.23-1.26 (m, 18H), 1.51 (t, 2H, J ¹² = 6.3 Hz), ^3.21-3.28 (m, 2H), 5.41 (s, 2H), 6.83 (d, 1H, J = 9.0 Hz), 6.98 (dd , 1H, ^J12 = 8.7 Hz, J13 = 3.0 Hz), 7.19 ⁽ d, 1H, J13 = 3.0 Hz), 7.54 (d, 2H, ^J12 = ^8.1 Hz), 7.86 (d, 2H, ^J12 = 8.1 Hz), 8.46 (t, 1H, ^J12 = 5.6 Hz), 9.20 (s, 1H), 9.89 (s, 1H).

Step 2: Synthesis of Monomer M-15 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-dodecylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 114.69 mmol, m=24.15 gr) in 1.2 L of acetonitrile, intermediate I-15 (2,5-dihydroxybenzoic acid 4- dodecylcarbamoylbenzoyl ester) (mw = 455.60 g/mol, 54.61 mmol, m = 24.88 gr), and triethylamine (mw = 101.19 g/mol, 117.40 mmol, m = 11.88 gr) were charged and the monomer M- 1 to give the monomer M-15. After the reaction is finished, the solution is filtered to remove insoluble matter, concentrated to 0.4 L volume, and allowed to stand for 2 days to form a precipitate. The solid is filtered and washed with a small amount of acetonitrile. The crude product was recrystallized twice with a mixture of acetonitrile (300 mL) and acetic anhydride (15 mL) followed by addition of charcoal during the second recrystallization and drying at 85° C. under vacuum for 24 hours. to obtain monomer M-15 in the form of a white solid. m=10.28 gr (mw=803.83 g/mol, 12.78 mmol), yield 23.4%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.82-0.87 (m, 3H), 1.20-1.30 (m, 18H), 1.50 (m, 2H), ^3.17-3.21 (m, 2H), 5.24 (s, 2H), 7.31 (d, 2H, J = 8.1 Hz), 7.57 (d, 2H, J = ⁸ .4 Hz), 7.64 (d, 2H, J = 9.0 Hz), 7.85 ⁽ dd, 1H, J = ^8.7 Hz, J = 2.7 Hz), ^8.12-8.17 (m, 2H), 8.28-8.35 (m, 3H), 8.44 (dd, 1H, J = 7.8 Hz, J = ^1.2 Hz), ^8.65-8.68 ( m, 2H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (317.2°C); DSC (heating 10°C/min, N ₂ atmosphere): mp = 172.3°C.

Example 16: Synthesis of Monomer M-16 Compound M-16 was prepared according to Reaction Scheme M-16 below, and the method for preparing intermediate I-16 and final product compound M-16 was described in steps 1 and 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-16 (2,5-Dihydroxybenzoic acid 4-hexadecylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 198.93 mmol, m=30.66 gr), 4-chloromethyl- N-hexadecylbenzamide (4-chloromethyl-N-hexadecylbenzamide) (mw = 394.04 g/mol, 195.03 mol, m = 76.85 gr) and potassium bicarbonate (mw = 100.12 g/mol, 390.06 mmol) , m=39.05 gr) and reacted at 65° C. for 24 hours under nitrogen atmosphere to obtain intermediate I-16 analogously to intermediate I-1. After the reaction is finished, the mixture is put into 3 L of water and the precipitated white solid is filtered and washed with water. The crude product is suspended in hot water at 80° C. and stirred for 30 minutes before filtering. The resulting solid is dried in air for 24 hours and then dried at 90° C. under reduced pressure for 24 hours. The product is obtained as a white solid.

_Rf = 0.30 (eluent ethylacetate: hexane = 1:2, TLC silica _gel60F254 ), m = 95.4 gr (mw = 511.7 g/mol, 186.44 mmol), yield 95.6%.
mp = 118-120°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.82-0.87 (m, 3H), 1.16-1.27 (m, 26H), 1.48-1.52 (m , 2H), ^3.21-3.29 (m, 2H), 5.41 (s, 2H), 6.83 (d, 1H, J = 9.0 Hz), 6.98 (dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 7.19 ⁽ d, 1H, J13 = 3.0 Hz), 7.54 (d, 2H, ^J12 = ^8.1 Hz), 7.86 (d, 2H, ^J12 = 8.1 Hz), 8.46 (t, 1H, ^J12 = 5.6 Hz), 9.21 (s, 1H), 9.90 (s, 1H).

Step 2: Synthesis of Monomer M-16 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-hexadecylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 390.28 mmol, m=82.18 gr) in 1.5 L of acetonitrile, intermediate I-16 (2,5-dihydroxybenzoic acid 4- hexadecylcarbamoylbenzoyl ester) (mw = 511.70 g/mol, 185.85 mmol, m = 95.1 gr) and triethylamine (mw = 101.19 g/mol, 408.87 mmol, m = 41.37 gr) were added to react, Monomer M-16 is prepared in a manner analogous to monomer M-1. After the reaction is over, the resulting solution is filtered to remove insoluble material, concentrated to 0.5 L volume and then diluted with 1.5 L of water. The solid is filtered and washed with water. The resulting solid is dried in air for 24 hours and then at 80° C. under reduced pressure for 24 hours. The crude product is recrystallized twice with a mixture of acetonitrile (600 mL) and acetic anhydride (100 mL), and the second time is dried under vacuum at 80° C. for 24 hours with the addition of charcoal. The product monomer M-16 was obtained as a white solid. m=88.7 gr (mw=859.94 g/mol, 103.15 mmol), yield 55.5%.

¹ H NMR (CDCl ₃ ) 300 MHz, δ, ppm: 0.87-0.92 (m, 3H), 1.16-1.36 (m, 26H), 1.60-1.64 (m, 2H) ), 3.41-3.48 (m, 2H), 5.24 (s, 2H), 6.13 (t, 1H, J = 5.4 Hz), 7.25-7.38 (m, 3H ), 7.51-7.63 (m, 3H), 8.04-8.10 (m, 2H), 8.22 (d, 1H, J = ^8.1Hz ), 8.53-8. 56 (m, 2H), 8.75 (dd, 1H, J12 = ^8.1Hz , J13 = ^1.5Hz ), 8.84 (s, 1H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (263.4°C); DSC (heating 10°C/min, N ₂ atmosphere): mp = 155.0°C.

Example 17: Synthesis of Monomer M-17 Compound M-17 was prepared according to the following Reaction Scheme M-17, and the process for preparing intermediate I-17 and final product compound M-17 was described in Step 1 and Step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-17 (2,5-Dihydroxybenzoic acid 4-(4-octylphenylcarbamoyl) benzyl ester (1:2 mixture of conformers)):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 117.12 mmol, m=18.05 gr), 4-chloromethyl- N-(4-octylphenyl)benzamide (4-chloromethyl-N-(4-octylphenyl)benzamide) (mw = 357.93 g/mol, 113.71 mol, m = 40.7 gr), and potassium hydrogen carbonate (mw = 100.12 g/mol, 227 mmol, m=22.72 gr), reacted at 65° C. for 24 hours under nitrogen atmosphere to prepare intermediate I-17 in a similar manner to intermediate I-1. After the reaction was completed, the mixture was put into 1.5 L of water and the precipitated white solid was filtered, washed with water, purified twice by resuspending and boiling with 0.5 L of methanol, and Cool to 30° C. and filter the solids.

The product is dried at 80° C. under vacuum for 24 hours to obtain a white solid.

_Rf = 0.38 (eluent ethylacetate: hexane = 1:2, TLC silica _gel60F254 ), m = 44.87 gr (mw = 475.59 g/mol, 94.35 mmol), yield 83%.
mp = 136°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.85 (t, 4.5H, J=6.7Hz), 1.20-1.30 (m, 15H), 1.50-1 .60 (m, 3H), 2.50-2.55 (m, 3H), 4.84 (s, 1H, CH ₂ ), 5.45 (s, 2H, CH ₂ ), 6.85 (d , 1H, ^J12 = 8.7 Hz), 6.99 (dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 7.15 ⁽ d, 3H, ^J12 = 8.4 Hz), 7.20 (d, 1H, J = ^3.0Hz ), 7.57-7.68 (m, 6H), 7.93-7.99 (m, 3H), 9.24 (s, 1H) , 9.90 (br s, 1H), 10.19 (s, 1.5H).

Step 2: Synthesis of monomer M-17 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-4-octylphenylcarbamoyl) benzyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 196.5 mmol, m=41.38 gr), intermediate I-17 (2,5-dihydroxybenzoic acid 4-(4 -octylphenylcarbamoyl) benzoyl ester) (mw = 475.59 g/mol, 93.67 mmol, m = 44.5 gr) and triethylamine (mw = 101.19 g/mol, 205.85 mmol, m = 20.83 gr). reacted to obtain monomer M-17 in a manner analogous to monomer M-1. After the reaction is completed, the brown solution is filtered under hot conditions to remove insoluble matter and cooled to room temperature. Precipitation of solids begins almost immediately from the hot solution state. The solid is filtered and washed with a small amount of acetonitrile. The crude product is purified by suspending it in a mixture of acetonitrile (800 mL) and acetic anhydride (50 mL) followed by boiling, then cooling to ambient temperature and filtering the solid. The product is obtained by drying at 100° C. under vacuum for 24 hours. The product, monomer M-17, is a yellowish crystalline solid. m = 32.77 gr (mw = 823.82 g/mol, 39.78 mmol), yield 42.5%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.85 (m, 3H), 1.20-1.30 (m, 10H), 1.50-1.60 (m, 2H), 2.50-2.57 (m, 2H), 5.29 (s, 2H, _CH2 ), 7.15 (d, 1H, J= ^8.7Hz ), 7.40 (d, 1H, J ¹² = 8.1 Hz), 7.61-7.72 (m, 5H), 7.83-7.88 (m, 1H), 8.17-8.19 (m, 2H), 8.29 ( d, 1H, J = ^8.4Hz ), 8.39-8.40 (m, 1H), 8.47-8.50 (m, 1H), 8.65-8.69 (m, 1H) , 10.06 (s, 1H, NH).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (320.3°C); DSC (heating 10°C/min, N ₂ atmosphere): mp = 230.1°C.

Example 18: Synthesis of Monomer M-18 Compound M-18 was prepared according to Reaction Scheme M-18 below, and the method for preparing intermediate I-18 and final product compound M-18 was described in Step 1 and Step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-18 (2,5-Dihydroxybenzoic acid 4-N,N-dibutylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 99.35 mmol, m=15.31 gr), N,N-dibutyl in 0.2 L of dimethylacetamide (DMAC) -4-chloromethylbenzamide (N,N-dibutyl-4-chloromethylbenzamide) (mw = 281.83 g/mol, 99.35 mol, m = 33.17 gr), and potassium hydrogen carbonate (mw = 100.12 g/mol, 200 mmol, m=20.02 gr), and reacted at 65° C. for 24 hours under a nitrogen atmosphere to synthesize intermediate I-18 in a similar manner to intermediate I-1. After the reaction was completed, the mixture was put into 1.5 L of water and the precipitated white sticky solid was filtered, washed with water, dried and crystallized with about 400 mL of hexane/dichloromethane. The white crystalline material is filtered, washed with hexane and dried at 80° C. under reduced pressure for 24 hours. The final product is a white crystalline solid. _Rf = 0.23 (eluent ethylacetate: hexane = 1:2, TLC silica _gel60F254 ), m = 31.4 gr (mw = 399.49 g/mol, 78.60 mmol), yield 79.1%.

mp = 117-119°C.
¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.65-0.75 (m, 3H), 0.88-0.98 (m, 3H), 1.00-1.12 (m , 2H), 1.27-1.37 (m, 2H), 1.39-1.49 (m, 2H), 1.51-1.61 (m, 2H), 3.09-3.19 (m, 2H), ^3.35-3.45 (m, 2H), 5.40 (s, 2H), 6.83 (d, 1H, J = 9.0 Hz), 6.98 (dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 7.19 ⁽ d, 1H, J13 = 3.0 Hz), 7.36 ⁽ d, 2H, J12 = 8.4 Hz), ⁷ .53 (d, 2H, J12 = ^8.4Hz ), 9.24 (br s, 1H), 9.89 (br s, 1H).

Step 2: Synthesis of Monomer M-18 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-N,N-dibutylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 164.13 mmol, m=34.56 gr), intermediate I-18 (2,5-dihydroxybenzoic acid 4-N, N-dibutylcarbamoylbenzoyl ester) (mw = 399.49 g/mol, 78.15 mmol, m = 31.22 gr) and triethylamine (mw = 101.19 g/mol, 168 mmol, m = 17 gr) were added to react, and the monomer M Monomer M-18 is obtained in an analogous manner to -1. After the reaction is finished, the brown solution is filtered hot to remove insoluble matter, and the solution is concentrated to 0.4 L volume. A white solid precipitates almost immediately from the hot solution. The solid is filtered and washed with a small amount of acetonitrile. After recrystallizing the crude product twice from a mixture of acetonitrile (500 mL) and acetic anhydride (30 mL), the product is dried under vacuum at 85° C. for 24 hours to give monomer M-18 as a white crystalline solid. . m = 35.09 gr (mw = 747.72 g/mol, 46.93 mmol), yield 60.5%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.62-0.72 (m, 3H), 0.90-1.08 (m, 5H), 1.25-1.60 (m , 6H), 3.00-3.10 (m, 2H), ^3.35-3.45 (m, 2H), 5.24 (s, 2H), 7.11 (d, 2H, J = 8.1 Hz), 7.32 (d, 2H, ^J12 = 8.1 Hz), 7.65 (d, 1H, ^J12 = 8.7 Hz), 7.85 (dd, 1H, ^J12 = 9.1 Hz). 0Hz, J13 = ^3.0Hz ), 8.15 (d, 1H, J13 = ^3.0Hz ), 8.19 (d, 1H, J12 = ^7.8Hz ), 8.29 (d, 1H, J = 8.4 Hz), 8.40 (br s, 1H), 8.49 (dd, 1H, J = ^7.8 Hz, J = 1.5 Hz), ^{8.65-8.68 (} m , 2H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (332.8°C); DSC (heating 10°C/min, N ₂ atmosphere): mp = 180.0°C.

Example 19: Synthesis of Monomer M-19 Compound M-19 was prepared according to Reaction Scheme M-19 below, and the process for preparing intermediate I-19 and final product Compound M-19 was described in Step 1 and Step 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-19 (2,5-Dihydroxybenzoic acid 4-N,N-dioctylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 166.57 mmol, m=25.67 gr), N,N-dioctyl in 0.35 L of dimethylacetamide (DMAC) -4-chloromethylbenzamide (N,N-dioctyl-4-chloromethylbenzamide) (mw = 394.04 g/mol, 163.31 mol, m = 64.35 gr) and potassium hydrogen carbonate (mw = 100.12 g/mol, 326.62 mmol, m=32.70 gr), and reacted at 65° C. for 24 hours under a nitrogen atmosphere to synthesize intermediate I-19 in a similar manner to intermediate I-1. After the reaction was completed, the mixture was put into 2 L of water and the precipitated oil was extracted with ethyl acetate (1 L). The organic layer was washed with aqueous hydrocarbon and water three times, then dried over aqueous sodium sulfate. Ethyl acetate is evaporated under pressure and the oily residue is dissolved in hot hexane (0.7 L), treated with silica gel and filtered under hot conditions to remove impurities. Hexane is evaporated under reduced pressure to give a colorless sticky oil. _Rf = 0.48 (eluent ethylacetate: hexane = 1:2, TLC silica _gel60F254 ), m = 67.8 gr (mw = 511.71 g/mol, 132.50 mmol), yield 81.1%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 0.80-0.86 (m, 6H), 1.03-1.56 (m, 20H), 1.44-1.56 (m , 4H), 3.13 (s, 2H), 3.29 (s, 2H), 5.40 (s, 2H), 6.83 (d, 1H, J = 9.0 Hz), ^6.98 (dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 7.19 ⁽ d, 1H, J13 = 3.0 Hz), 7.36 ⁽ d, 2H, ^J12 = 8.4 Hz ), 7.53 (d, 2H, ^J12 = 8.4 Hz), 9.20 (s, 1H), 9.91 (s, 1H).

Step 2: Synthesis of Monomer M-19 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-N,N-dioctylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 277.43 mmol, m=58.24 gr) in 1.2 L of acetonitrile, intermediate I-19 (2,5-dihydroxybenzoic acid 4- N,N-dioctylcarbamoylbenzoyl ester) (mw = 511.71 g/mol, 132.11 mmol, m = 67.6 gr) and triethylamine (mw = 101.19 g/mol, 290.64 mmol, m = 29.41 gr) were added. to synthesize monomer M-19 in a similar manner to monomer M-1. After the reaction is finished, the brown solution is filtered hot to remove insoluble material and concentrated to 0.5 L volume. After cooling the solution to room temperature, a white solid is formed. The solid is filtered and washed with a small amount of acetonitrile. The crude product is recrystallized twice with a mixed solvent of acetonitrile (600 mL) and acetic anhydride (30 mL), after which decolorizing charcoal is added during the second recrystallization. The product is dried under vacuum at 90° C. for 24 hours to give monomer M-19 as a white crystalline solid as the final product. m=71.4 gr (mw=859.94 g/mol, 83.03 mmol), yield 62.8%.

¹ H NMR (CDCl ₃ ) 300 MHz, δ, ppm: 0.82-0.91 (m, 6H), 1.09-1.63 (m, 24H), 3.08-3.14 (m, 2H) ), ^3.41-3.47 (m, 2H), 5.23 (s, 2H), 7.15 (d, 2H, J = 8.1 Hz), 7.29 (d, ^2H , J = 8.1 Hz), 7.36 (d, 1H, ^J12 = 8.7 Hz), 7.60 ⁽ dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 8.06 (d , 1H, J13 = 3.0 Hz), 8.11 ⁽ d, 1H, ^J12 = 7.8 Hz), 8.22 (d, 1H, ^J12 = 8.1 Hz), 8.53 (dd, 1H , J ¹² =7.8 Hz, J ¹³ =1.5 Hz), 8.59 (s, 1H), 8.76 (dd, 1H, J ¹² =8.1 Hz, J ¹³ =1.5 Hz), 8. 85 (s, 1H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (293°C); DSC (heating 10°C/min, N ₂ atmosphere): mp = 182.7°C.

Example 20: Synthesis of Monomer M-20 Compound M-20 was prepared according to the following Reaction Scheme M-20, and the method for preparing intermediate I-20 and final product compound M-20 was described in steps 1 and 2, respectively. Separately detailed below:

Step 1: Synthesis of intermediate I-20 (2,5-Dihydroxybenzoic acid 4-N,N-dibenzylcarbamoylbenzoyl ester):
2,5-dihydroxybenzoic acid (mw=154.12 g/mol, 128.24 mmol, m=19.76 gr), N,N-dibenzyl in 0.2 L of dimethylacetamide (DMAC) -4-chloromethylbenzamide (N,N-dibenzyl-4-chloromethylbenzamide) (mw = 349.86 g/mol, 124.51 mol, m = 43.56 gr) and potassium bicarbonate (mw = 100.12 g/mol, 249.02 mmol, m = 24.93 gr) and reacted at 65°C for 24 hours under a nitrogen atmosphere to synthesize intermediate I-20 in a similar manner to intermediate I-1. After the reaction was completed, the mixture was added to 1 L of water and the precipitated solid was filtered and crystallized twice with 400 mL of methanol. The product is dried at 70° C. under reduced pressure for 12 hours. The resulting product intermediate I-20 was a white solid, R _f =0.25 (eluent ethylacetate:hexane=1:2, TLC silica gel 60 F ₂₅₄ ), mp=90-92° C., m= 41.73 gr (mw=467.52 g/mol, 89.26 mmol), yield 71.7%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 4.41 (s, 2H), 4.59 (s, 2H), 5.38 (s, 2H), 6.83 (d, 1H, J ¹² =9.0 Hz), 6.98 (dd, 1H, J ¹² =9.0 Hz, J ¹³ =3.0 Hz), 7.14-7.19 (m, 3H), 7.26-7. 36 (m, 8H), 7.53 (s, 4H), 9.20 (s, 1H), 9.90 (bs, 1H).

Step 2: Synthesis of Monomer M-20 (Bis-trimellitic acid anhydride ester of 2,5-dihydroxybenzoic acid 4-N,N-dibenzylcarbamoylbenzoyl ester):
Trimellitic anhydride chloride (mw=210.57 g/mol, 186.59 mmol, m=39.29 gr), intermediate I-20 (2,5-dihydroxybenzoic acid 4-N, N-dibenzylcarbamoylbenzoyl ester) (mw = 467.52 g/mol, 88.85 mmol, m = 41.54 gr) and triethylamine (mw = 101.19 g/mol, 195.47 mmol, m = 19.78 gr) were added to the reaction. to synthesize monomer M-20 in a similar manner to monomer M-1. After the reaction is finished, the brown solution is filtered hot to remove insoluble material and concentrated to 0.5 L volume. After cooling to ambient temperature, a white solid is produced. The solid is filtered and washed with a small amount of acetonitrile. After recrystallizing the crude product twice with a mixture of acetonitrile (500 mL) and acetic anhydride (50 mL), the product was dried under vacuum at 80° C. for 24 hours to give the final product of monomer M-20 as a white crystalline Obtained as a solid. m = 45.36 gr (mw = 815.75 g/mol, 55.61 mmol), yield 62.6%.

¹ H NMR (DMSO-d ₆ ) 300 MHz, δ, ppm: 4.31 (s, 2H), 4.54 (s, 2H), 5.22 (s, 2H), 7.11-7.35 ( m, 14H), 7.64 (d, 1H, ^J12 = 9.0 Hz), 7.84 ⁽ dd, 1H, ^J12 = 9.0 Hz, J13 = 3.0 Hz), 8.15 (d, 1H, J13 = 3.0 Hz), 8.19 (d, 1H, ^J12 = ^8.1 Hz), 8.29 (d, 1H, ^J12 = 8.1 Hz), 8.42 (s, 1H) , 8.48 (dd, 1H, J ¹² =7.8 Hz, J ¹³ =1.2 Hz), 8.64-8.67 (m, 2H).
Thermal analysis: TGA (heating 10°C/min, N ₂ atmosphere): 1 wt% loss (333.7°C); DSC (heating 10°C/min, N ₂ atmosphere): mp = 225.9°C.

Production Examples: Synthesis of Polymer and Production of Film Production Examples 1-1 to 1-8: Synthesis of Polyester-imide and Production of Film Monomer M-1 produced in Example 1 was mixed in proportions as described in Table 1 below. with additional dianhydrides 6FDA or BPDA and with TFDB and/or DADPS as diamines to prepare polyester-amic acids.

Specifically, after dissolving 1 equivalent of diamine TFDB and/or DADPS in a dry solvent DAMc, this solution was added with the monomer M-1 prepared in Example 1 as a dianhydride in the ratio described in Table 1 below. After adding a total of 1 equivalent of the mixture of additional dianhydrides mixed with 6FDA or BPDA, the mixture is stirred at 25° C. for 24 hours to obtain polyester-amic acid solutions according to Preparation Examples 1-1 to 1-8. A chemically partially imidized polyester-imide solution is obtained by stirring the resulting polyamic acid solution with an additional 3 equivalents of acetic anhydride and 3 equivalents of pyridine at 25° C. for 12 hours.

The prepared polyester-imide solution is spin-coated onto a 50×50 mm glass substrate at a speed of 1,000 rpm to 3,000 rpm. After the coated film was dried on a hot plate set at 80°C for 30 minutes, it was heated in a furnace at a heating rate of 10°C/min from about 25°C to about 230°C. and isothermally treated at 230° C. for 30 minutes to produce the film.

Production Example 2 to Production Example 11
A dianhydride mixture obtained by mixing monomers M-2 to M-14 produced in Examples 2 to 14 in place of the monomer M-1 produced in Example 1 with 6FDA at the ratio shown in Table 1 below, and a diamine According to Preparation Examples 2 to 11, the same method as in Preparation Examples 1-1 to 1-8 was used, except that TFDB was reacted at a molar ratio of 1:1 to prepare polyester-amic acid. A polyester-imide film was obtained.

Production Example 12 to Production Example 17
A dianhydride mixture obtained by mixing monomers M-15 to M-20 produced in Examples 15 to 20 in place of the monomer M-1 produced in Example 1 with 6FDA at the ratio shown in Table 1 below, and a diamine The polyesters of Preparation Examples 12 to 17 were prepared in the same manner as in Preparation Examples 1-1 to 1-8, except that the polyester-amic acid was prepared by reacting TFDB at a molar ratio of 1:1. An imide solution was prepared.

The prepared polyester-imide solution was precipitated in distilled water, pulverized with a mixer, and washed with ethanol. The white precipitate is filtered, dried in an 80° C. oven overnight, and redissolved in cyclopentanone (CP).

The resulting polyester-imide solution in CP is spin-coated onto a 50×50 mm glass substrate at a speed of 1,000 rpm to 3,000 rpm. After the coated film was dried on a hot plate set at 80°C for 30 minutes, it was heated in a furnace at a heating rate of 10°C/min from about 25°C to about 170°C. Films are produced by heating and isothermal treatment at 170° C. for 120 minutes.

Comparative Production Example 1 and Comparative Production Example 2
Without using any of the monomers M-1 to M-20 produced in Examples 1 to 20, 6FDA alone as a dianhydride and TFDB alone as a diamine were reacted at a ratio of 1:1 to produce a polyimide. Comparative Production Example 1 is a film produced in the same manner as in Production Examples 1-1 to 1-8 except that the film was produced.

In addition, 6FDA and TAHQ (hydroquinone bis (trimellitate dianhydride)) were used as a dianhydride in a mixture at the content ratio shown in Table 1 below, and TFDB was used alone as a diamine and reacted at a ratio of 1:1 to prepare a polyimide. Comparative Production Example 2 is a film produced in the same manner as in Production Examples 1-1 to 1-8 except for the above.

Evaluation Composition and intrinsic viscosity (Inherent viscosity: η ), thickness, transmittance (%), yellowness index (YI), thickness direction retardation (out-of-plane birefringence Δn _th ), and glass transition temperature (Glass transition temperature: Tg) are shown in Table 1 below. . The methods for measuring the thickness, through-thickness birefringence, transmittance and yellowness index, and glass transition temperature of the film are respectively as follows:

(1) Film thickness was measured using Filmetrics F20 (Filmetrics, Inc., Kanagawa, Japan).
(2) The out-of-plane birefringence Δn _th of the film is measured using a prism coupler (Metricon MODEL 2010/M) at 450 nm wavelength.
(3) Film optical properties (transmittance and yellowness index) are measured using a "Konica Minolta CM3600d" spectrophotometer in transmittance opacity/haze mode.
(4) Intrinsic viscosity is measured using a Cannon PolyVisc Automated Viscosimeter on a 0.5 g/dL polymer solution in DMAc.
(5) Glass transition temperature (Tg) is measured using a thermal mechanical analyzer (TMA Q400, TA Instruments) at a fixed tension force of 0.05 N, and 5 It is measured in a temperature range of 50° C. to 400° C. at a heating rate of ° C./min.

As can be seen from Table 1, films made from polyester-imides made with ester group-containing dianhydrides according to one embodiment have high transmittance at 450 nm, low yellowness index, and low haze, Also, by exhibiting very high values of through-thickness birefringence, from a minimum of about 0.04 to a maximum of about 0.09, polyester-imide films made from ester group-containing dianhydros according to one embodiment have excellent optical properties. Are better. In addition, it can be seen that the glass transition temperature has a value above a certain range, so that it has high thermal stability. That is, the film produced from an ester group-containing aromatic dianhydride and an aromatic diamine according to one embodiment has conventional high thermal stability and excellent optical properties as in Comparative Production Example 1 or Comparative Production Example 2. By exhibiting equal or better optical properties while having equal or better thermal stability compared to polyimide films produced using specific aromatic dianhydrides and aromatic diamines known to , reacting a novel dianhydride containing an ester group according to one embodiment with a specific aromatic dianhydride known to have excellent conventional optical properties and high thermal stability, or alternatively with an aromatic diamine. It can be seen that a film with excellent optical properties and thermal stability can be produced. The ester group-containing dianhydride according to one embodiment can be produced at a lower production cost than conventional aromatic dianhydrides exhibiting excellent optical properties and thermal stability. The manufacturing cost can be significantly reduced while still having excellent optical properties and thermal stability.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims, the detailed description of the invention, and the accompanying drawings. is possible and also falls within the scope of the present invention.

100: Optical film 110: Polarizer 120: Compensation film 50: Display panel 400: Organic light-emitting display panel 410: Base substrate 420: Lower electrode 430: Organic light-emitting layer 440: Upper electrode 450: Sealing substrate 500: Liquid crystal display panel 510 : First display panel 520: Second display panel 530: Liquid crystal layer

Claims (20)

A monomer represented by Chemical Formula 1 below:

In the above chemical formula 1,
R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted 1 to 30 carbon atoms an alkoxy group of, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), -SiR'R"R"' (where R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms) , or a combination thereof, and
o and p are each independently an integer from 0 to 3;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 carbon atoms,
R ^a is hydrogen, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, substituted or an unsubstituted cycloalkyl group having 3 to 30 carbon atoms , a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, -NR'R" (where, R' and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), —CO—NR′R″ (where R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms),— SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 to 30 arylalkyl groups), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 30 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; can be,
q and r are each independently an integer from 0 to 3;
m is an integer from 0 to 3,
n is an integer from 1 to 20; o and p in Chemical Formula 1 are each independently 0 or 1, L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms), and A ¹ is an aromatic organic group having 6 carbon atoms, R ^a is hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted an arylalkyl group having 7 to 20 carbon atoms, a halogen group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, a or an arylalkyl group having 7 to 30 carbon atoms), -CO-NR'R" (wherein R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), -SiR'R"R"' (wherein R', R", and R"' are each independently is hydrogen or an alkyl group having 1 to 20 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; is, q and r are each independently an integer of 0 to 2, and 1 ≤ q + r ≤ 2;
m is 0-2 and n is an integer of 1-10 . o and p in Chemical Formula 1 are each independently 0 or 1, L ¹ is O or NH, A ¹ is a benzene ring, R ^a is hydrogen, substituted or unsubstituted C 1 to 20 alkyl groups, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, halogen groups, —CO—NR′R″ (wherein R′ and R″ are respectively independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2, A monomer according to claim 1:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted benzene ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m is 0 or 1 and n is an integer of 1-5 . The monomer according to claim 1, wherein the monomer represented by Chemical Formula 1 is a monomer represented by Chemical Formula 3 or a monomer represented by Chemical Formula 4 below:

In the above chemical formulas 3 and 4,
R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted 1 to 30 carbon atoms an alkoxy group of, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a hydroxy group, a halogen group, a nitro group, —NR′R″ (wherein R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms), -SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms), or a combination thereof;
o and p are each independently an integer from 0 to 3;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 carbon atoms,
R ^a is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkoxy group having 3 to 30 carbon atoms, a substituted or unsubstituted substituted or unsubstituted C3-30 cycloalkyl group , substituted or unsubstituted C7-30 arylalkyl group, hydroxy group, halogen group, nitro group, —NR′R″ (where R′ and R ″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), —CO—NR′R” (here and R′ and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), —SiR′ R″R″ (wherein R′, R″, and R″ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 30), or a group represented by the following chemical formula 2:

L ² and L ³ are each independently O, CO, COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 30 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 30 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms; can be,
q and r are each independently an integer from 0 to 3;
m is 0 to 3,
n is an integer from 1 to 20; o and p in Chemical Formulas 3 and 4 are each independently 0 or 1;
L ¹ is O or NR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ¹ is an aromatic organic group having 6 carbon atoms,
R ^a is hydrogen, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms, halogen -NR'R" (where R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms is an alkyl group), -CO-NR'R" (wherein R' and R" are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or carbon an arylalkyl group having a number of 7 to 30), -SiR'R"R"' (wherein R', R", and R"' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms) , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted aromatic ring having 6 to 20 carbon atoms, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms; can be,
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m is 0 or 1 and n is an integer of 1-10 . o and p in Chemical Formula 3 and Chemical Formula 4 are all 0, L ¹ is O or NH, A ¹ is a benzene ring, R ^a is hydrogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms; group, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, halogen group, —CO—NR′R″ (wherein R′ and R″ are each independently hydrogen, alkyl having 1 to 30 carbon atoms, , an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms), or a group represented by the following chemical formula 2:

In the above chemical formula 2,
L ² and L ³ are each independently COO, C≡C, or CONR ^b (wherein R ^b is hydrogen or an alkyl group having 1 to 20 carbon atoms);
A ² and A ³ are each independently a substituted or unsubstituted benzene ring, a substituted or unsubstituted fluorene ring, or a substituted or unsubstituted arylalkyl group having 7 to 20 carbon atoms;
q and r are each independently an integer of 0 to 2 and 1 ≤ q + r ≤ 2;
m is 0 or 1 and n is an integer of 1-5 . A polymer which is the product of a reaction comprising a monomer according to any one of claims 1-6 and a diamine. The polymer according to claim 7, wherein the diamine is represented by Formula 5 below:
[Chemical Formula 5]
_{NH2 -} Rc- ^NH2
In the above chemical formula 5,
R ^c includes a substituted or unsubstituted aromatic organic group having 6 to 30 carbon atoms, and the substituted or unsubstituted aromatic organic group having 6 to 30 carbon atoms exists as one substituted or unsubstituted aromatic ring. two or more substituted or unsubstituted aromatic rings are joined together to form a condensed ring; or two or more rings selected from said one aromatic ring and/or said condensed ring are singly a bond, or a fluorenylene group, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted arylene group having 6 to 15 carbon atoms, -O-, -S-, -C(=O)- , —CH(OH)—, —S(=O) ₂ —, —Si(CH ₃ ) ₂ —, —(CH ₂ ) _p — (where 1≦p≦10), —(CF ₂ ) _q - (where 1≤q≤10), -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -C(=O)NH-, or combinations thereof. be. The polymer according to claim 8, wherein the diamine represented by Chemical Formula 5 is represented by one or more of Chemical Formulas 6 to 8 below:

In the above chemical formula 6,
R ^d is selected from the group consisting of:

R ⁷ and R ⁸ are the same or different from each other, and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²⁰⁰ , where R ²⁰⁰ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰¹ R ²⁰² R ²⁰³ , wherein R ²⁰¹ , R ²⁰² and R ²⁰³ are the same or different and each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or an aromatic organic group having 6 to 20 carbon atoms,
n1 and n2 are each independently an integer from 0 to 4;
* indicates a connecting point;

In the above chemical formula 7,
R ²⁶ and R ²⁷ are the same or different and each independently -CF ₃ , -CCl ₃ , -CBr ₃ , -CI ₃ , -NO ₂ , -CN, -COCH ₃ or -CO ₂ an electron withdrawing group _selected from _C2H5 ;
R ²⁸ and R ²⁹ are the same or different from each other and are each independently a halogen, a hydroxy group, an alkoxy group (-OR ²⁰⁴ , where R ²⁰⁴ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰⁵ R ²⁰⁶ R ²⁰⁷ , wherein R ²⁰⁵ , R ²⁰⁶ and R ²⁰⁷ are the same or different and each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n3 is an integer of 1 to 4, n5 is an integer of 0 to 3, n3+n5 is an integer of 1 to 4,
n4 is an integer from 1 to 4, n6 is an integer from 0 to 3, and n4+n6 is an integer from 1 to 4;

In the above chemical formula 8,
R ¹⁴ is O, S, C(=O), CH(OH), S(=O) ₂ , Si(CH ₃ ) ₂ , (CH ₂ ) _p (where 1 ≤ p ≤ 10), (CF ₂ ) _q , where 1≦q≦10, C(CH ₃ ) ₂ , C(CF ₃ ) ₂ , C(═O)NH, or substituted or unsubstituted C 6-18 aromatic organic group, wherein said substituted or unsubstituted C6-C18 aromatic organic group is present as one substituted or unsubstituted aromatic ring; two or more substituted or unsubstituted aromatic rings are joined together form a condensed ring; or two or more rings selected from the one aromatic ring and/or the condensed ring are combined with a single bond, or a fluorenylene group, —O—, —S—, —C ( =O)-, -CH(OH)-, -S(=O) ₂ -, -Si(CH ₃ ) ₂ -, -(CH ₂ ) _p - (where 1≤p≤10), -( CF ₂ ) _q —, where 1≦q≦10, —C(CH ₃ ) ₂ —, —C(CF ₃ ) ₂ —, —C(=O)NH—, or combinations thereof; are linked by functional groups that
R ¹⁶ and R ¹⁷ are the same or different from each other, and are each independently a halogen, hydroxy group, alkoxy group (-OR ²¹² , where R ²¹² is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²¹³ R ²¹⁴ R ²¹⁵ , wherein R ²¹³ , R ²¹⁴ and R ²¹⁵ are the same or different from each other and are each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n9 and n10 are each independently an integer of 0-4. 10. The polymer of claim 9, wherein the diamine represented by Chemical Formula 5 includes at least one of the diamine represented by Chemical Formula 7 and the diamine represented by Chemical Formula 8. The diamine represented by Formula 7 includes 2,2′-bis(trifluoromethyl)benzidine (TFDB), and the diamine represented by Formula 8 is 4,4 11. The polymer of claim 10, comprising '-diaminodiphenyl sulfone (4,4'-diaminodiphenyl sulfone, DADPS). 8. The polymer of claim 7, which is a reaction product further comprising a dianhydride represented by Formula 9 below:

In the above chemical formula 9,
R ¹⁰ is a single bond, -O-, -S-, -C(=O)-, -CH(OH)-, -C(=O)NH-, -S(=O) ₂ -, - Si(CH ₃ ) ₂ -, -(CH ₂ ) _p -, -(CF ₂ ) _q -, -C(C _n H _2n+1 ) ₂ -, -C(C _n F _2n+1 ) ₂ -, -(CH ₂ ) _p —C(C _n H _2n+1 ) ₂ —(CH ₂ ) _q —, or —(CH ₂ ) _p —C(C _n F _2n+1 ) ₂ —(CH ₂ ) _q —, where 1≦n≦ 10, 1≤p≤10, and 1≤q≤10) groups;
R ¹² and R ¹³ each independently represent a halogen, a hydroxy group, a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms, - OR ²⁰¹ group (wherein R ²⁰¹ is an aliphatic organic group having 1 to 10 carbon atoms), or —SiR ²¹⁰ R ²¹¹ R ²¹² (wherein R ²¹⁰ , R ²¹¹ and R ²¹² are each independently hydrogen or an aliphatic organic group having 1 to 10 carbon atoms) group,
n7 and n8 are each independently one of the integers from 0 to 3; 13. The dianhydride according to claim 12, wherein the dianhydride represented by Chemical Formula 9 is a reaction product containing a dianhydride represented by Chemical Formula 10, a dianhydride represented by Chemical Formula 11, or a combination thereof. A polymer of:

In the above chemical formulas 10 and 11,
R ¹² and R ¹³ are the same or different from each other and are each independently a halogen, hydroxy group, alkoxy group (-OR ²⁰⁸ , where R ²⁰⁸ is an aliphatic organic group having 1 to 10 carbon atoms ), a silyl group (—SiR ²⁰⁹ R ²¹⁰ R ²¹¹ , wherein R ²⁰⁹ , R ²¹⁰ and R ²¹¹ are the same or different from each other and are each independently hydrogen, an aliphatic organic group having 1 to 10 carbon atoms ), a substituted or unsubstituted aliphatic organic group having 1 to 10 carbon atoms, or a substituted or unsubstituted aromatic organic group having 6 to 20 carbon atoms,
n7 and n8 are each independently an integer of 0-3. The polymer comprises the monomer according to any one of claims 1 to 6 and at least one of the dianhydride represented by the chemical formula 10 and the dianhydride represented by the chemical formula 11 . 14. The polymer of claim 13, which is the product of reactants in a molar ratio of 0:10 to 10:90. 8. The polymer according to claim 7, which is a reaction product further comprising a dicarboxylic acid derivative represented by the following chemical formula 12:

In the above chemical formula 12,
R ³ is a substituted or unsubstituted phenylene group and/or a substituted or unsubstituted biphenylene group, and each X is the same or different halogen atom. 16. The polymer according to claim 15, wherein R3 in Formula ¹² is an unsubstituted phenylene group and/or an unsubstituted biphenylene group, and each X is independently Cl or Br. A compensation film comprising a polymer according to any one of claims 7-16. 18. An optical film comprising the compensation film of claim 17 and a polarizer. A display device comprising the compensation film of claim 17. A display device comprising the optical film of claim 18 .

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